CN114349781A - 一种含手性四氢吡咯骨架氨基酚氧基锌络合物及其制备方法和应用 - Google Patents
一种含手性四氢吡咯骨架氨基酚氧基锌络合物及其制备方法和应用 Download PDFInfo
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- CN114349781A CN114349781A CN202210057511.1A CN202210057511A CN114349781A CN 114349781 A CN114349781 A CN 114349781A CN 202210057511 A CN202210057511 A CN 202210057511A CN 114349781 A CN114349781 A CN 114349781A
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- Prior art keywords
- zinc
- chiral
- aminophenoxy
- skeleton
- alkyl
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- 125000000719 pyrrolidinyl group Chemical group 0.000 title claims abstract description 31
- QNHGHNJBZCMVOX-UHFFFAOYSA-M N[Zn]OC1=CC=CC=C1 Chemical compound N[Zn]OC1=CC=CC=C1 QNHGHNJBZCMVOX-UHFFFAOYSA-M 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000010668 complexation reaction Methods 0.000 title description 2
- 239000011701 zinc Substances 0.000 claims abstract description 66
- 239000003446 ligand Substances 0.000 claims abstract description 43
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 9
- 150000002596 lactones Chemical class 0.000 claims abstract 5
- 239000003054 catalyst Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 48
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- -1 triethylsilyl Chemical group 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 20
- 125000004122 cyclic group Chemical group 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007858 starting material Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 125000003554 tetrahydropyrrolyl group Chemical group 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 150000001298 alcohols Chemical class 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
- 125000002496 methyl group Chemical group [H]C([H])([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
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 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 4
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 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 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 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 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- QXTIBZLKQPJVII-UHFFFAOYSA-N triethylsilicon Chemical compound CC[Si](CC)CC QXTIBZLKQPJVII-UHFFFAOYSA-N 0.000 claims description 2
- ZCCUYQBZUVUONI-UHFFFAOYSA-N zinc;bis(trimethylsilyl)azanide Chemical compound [Zn+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C ZCCUYQBZUVUONI-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000001914 filtration Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 abstract description 3
- QCTXENUBAFDBER-UHFFFAOYSA-N [O].NC1=C(C=CC=C1)O Chemical compound [O].NC1=C(C=CC=C1)O QCTXENUBAFDBER-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 83
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 36
- 238000009826 distribution Methods 0.000 description 36
- 238000003786 synthesis reaction Methods 0.000 description 34
- 239000002904 solvent Substances 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 22
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 239000003921 oil Substances 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- YOETUEMZNOLGDB-UHFFFAOYSA-N 2-methylpropyl carbonochloridate Chemical compound CC(C)COC(Cl)=O YOETUEMZNOLGDB-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 150000003335 secondary amines Chemical class 0.000 description 7
- 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 6
- 239000007832 Na2SO4 Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 3
- 238000012694 Lactone Polymerization Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229960002429 proline Drugs 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- ZQEBQGAAWMOMAI-ZETCQYMHSA-N (2s)-1-[(2-methylpropan-2-yl)oxycarbonyl]pyrrolidine-2-carboxylic acid Chemical compound CC(C)(C)OC(=O)N1CCC[C@H]1C(O)=O ZQEBQGAAWMOMAI-ZETCQYMHSA-N 0.000 description 2
- YIOLXYNYYMDFQD-JTQLQIEISA-N 1-methyl-2-[(2s)-pyrrolidin-2-yl]benzimidazole Chemical compound N=1C2=CC=CC=C2N(C)C=1[C@@H]1CCCN1 YIOLXYNYYMDFQD-JTQLQIEISA-N 0.000 description 2
- YTKAWFHOEDFUOP-VIFPVBQESA-N 2-[(2s)-pyrrolidin-2-yl]-1,3-benzothiazole Chemical compound C1CCN[C@@H]1C1=NC2=CC=CC=C2S1 YTKAWFHOEDFUOP-VIFPVBQESA-N 0.000 description 2
- XKEVDZMTMKDMAT-VIFPVBQESA-N 2-[(2s)-pyrrolidin-2-yl]-1,3-benzoxazole Chemical class C1CCN[C@@H]1C1=NC2=CC=CC=C2O1 XKEVDZMTMKDMAT-VIFPVBQESA-N 0.000 description 2
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 2
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 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 1
- 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 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- ZOBQXWFQMOJTJF-UHFFFAOYSA-N 2-n-benzylbenzene-1,2-diamine Chemical compound NC1=CC=CC=C1NCC1=CC=CC=C1 ZOBQXWFQMOJTJF-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- 239000011165 3D composite Substances 0.000 description 1
- 229930182821 L-proline Natural products 0.000 description 1
- YBDKTAWNNZGBSQ-UHFFFAOYSA-M NCC[Zn]OC1=CC=CC=C1 Chemical compound NCC[Zn]OC1=CC=CC=C1 YBDKTAWNNZGBSQ-UHFFFAOYSA-M 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
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- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 238000007430 reference method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- IPSRAFUHLHIWAR-UHFFFAOYSA-N zinc;ethane Chemical group [Zn+2].[CH2-]C.[CH2-]C IPSRAFUHLHIWAR-UHFFFAOYSA-N 0.000 description 1
Abstract
本发明公开了一类含手性四氢吡咯骨架氨基酚氧基锌络合物及其制备方法,以及其在高活性、高选择性催化内酯开环聚合中的应用。其制备方法包括:先将中性配体与金属原料化合物在有机介质中反应,然后经过滤、浓缩、重结晶步骤获得目标化合物。本发明的含手性四氢吡咯骨架氨基酚氧基锌络合物是一种高效的内酯开环聚合催化剂,可用于催化多种内酯开环聚合,其中催化外消旋丙交酯可获得高等规的聚丙交酯。本发明的含手性四氢吡咯骨架氨基酚氧基锌络合物优点十分明显:原料易得,合成路线简单,产物收率高,高催化活性和立体选择性,能获得高规整度和高分子量聚酯材料,满足工业部门的需要。其结构式如下所示:
Description
技术领域
本发明涉及一类含手性四氢吡咯骨架氨基酚氧基锌络合物,以及这类络合物在内酯聚合中的应用。
背景技术
由石油化工制得的聚烯烃类高分子材料应用于人类生活的各个方面,有限的石油资源和人们强烈的环保意识促进了可生物降解聚合物材料的快速发展。原料来自于可再生植物资源的聚丙交酯因具有良好的生物相容性、可降解性以及优异的机械加工性能将占据很大的市场,成为国内外研究的热点。这类脂肪族聚酯材料在自然界中经微生物介质分解产生二氧化碳和水,而二氧化碳又可用于植物的光合作用,故是一类用来替代石油基聚合物的环保节能型材料。聚丙交酯材料在医疗医药领域、建筑行业、食品包装、工农业生产中极具发展前景。
丙交酯是乳酸的环状二聚体,包括左旋丙交酯(L-Lactide)、右旋丙交酯(D-Lactide)、内消旋丙交酯(meso-Lactide)三种异构体,等比例左旋丙交酯和右旋丙交酯混合形成外消旋丙交酯(rac-Lactide)。可通过四种不同的催化方式实现丙交酯聚合:阴离子催化机制、阳离子催化机制、有机小分子催化机制和配位插入机制。以左旋或右旋丙交酯为单体,可以方便地聚合得到等规聚丙交酯,采用高等规选择性催化剂催化外消旋丙交酯聚合得到的等规嵌段聚丙交酯具有立体复合结构,比常规等规聚丙交酯具有更高的熔点和机械强度,因而受到广泛关注。近年来一些锌金属络合物在催化外消旋丙交酯聚合时展现出一定的等规选择性。锌元素是人体的必需元素,其离子无色、无毒,具有生物相容性,即使残留在聚合物中也对人体无害,符合聚丙交酯在食品包装及医药领域的应用要求,开发锌金属催化剂用于外消旋丙交酯开环聚合成为目前该领域的研究热点。
2003年,Tolman小组报道了多齿氨基酚配体配位的单乙氧基双核锌络合物催化外消旋丙交酯开环聚合,室温下该催化剂具有高催化活性,催化1当量单体聚合5分钟,转化率高达96%,但获得无规聚丙交酯(J.Am.Chem.Soc.2003,125,11350-11359)。2009年,Mehrkhodavandi小组报道了手性环己亚基取代氨基酚配体配位的锌乙基络合物催化外消旋丙交酯聚合,催化活性低,得到偏等规聚丙交酯,等规度Pm=0.54(Organometallics2009,28,1309-1319)。2013年,我们小组报道了具悬垂四氢吡咯配位的氨基酚氧基锌络合物,首次实现了金属锌络合物催化外消旋丙交酯聚合得到较高等规度的聚丙交酯,Pm=0.80(Chem.Commun.2013,49,8686-8688)。2014年,Du小组报道了一类含手性噁唑啉基团的类β-二亚氨基锌络合物催化外消旋丙交酯开环聚合,获得了等规立体嵌段聚丙交酯,Pm=0.91,但催化活性很低(ACS Macro Lett.2014,3,689-692)。2016年,Kol课题组用一系列四齿线型胺基酚氧基乙基锌络合物催化rac-LA聚合,有较好的等规选择性,室温下可达Pm=0.81(Chem.Eur.J.,2016,22:11533-11536)。2017年和2018年,我们小组分别报道了一系列手性噁唑啉和非手性苯并噁唑取代的氨基酚氧基锌络合物,能够高等规选择性催化外消旋丙交酯聚合,得到多嵌段等规聚丙交酯,Pm=0.89,且催化活性较高(Macromolecules2017,50,7911-7919;Inorg.Chem.2018,57,11240-11251)。2019年,我们小组进一步报道了非手性苯并咪唑取代的氨基酚氧基锌络合物,催化外消旋丙交酯开环聚合具有高催化活性和等规选择性,可获得高等规聚丙交酯,Pm=0.89(Chem.Commun.2019,55,10112-10115)。
人们在外消旋丙交酯等规聚合研究领域已经取得了一定的突破,通过对金属络合物催化剂结构进行有效设计获得了较高等规度的聚丙交酯。作为环境友好型聚合物,人们在筛选催化剂时更倾向于使用生物相容性的金属。目前对于锌金属络合物催化外消旋丙交酯聚合同时表现出了高等规选择性和较高催化活性的报道非常有限,有关锌金属络合物催化剂的研究工作仍有待于进一步开展,以合成集高活性、高等规选择性于一体的高效催化剂。
发明内容
本发明目的之一在于公开一类含手性四氢吡咯骨架氨基酚氧基锌络合物。
本发明目的之二在于公开一类含手性四氢吡咯骨架氨基酚氧基锌络合物的制备方法。
本发明目的之三在于公开一类含手性四氢吡咯骨架氨基酚氧基锌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:
手性脯氨酸属于天然产物,原料便宜易得,且便于构造具有一定刚性的手性配体骨架。四氢吡咯骨架中的固有手性结合金属中心的固有手性能够在金属周围形成更有效的不对称配位环境,期望在丙交酯单体与金属中心配位时起到手性诱导效果,从而达到立体选择性开环聚合得到等规聚丙交酯的目的。本发明在氨基酚类配体结构中引入手性四氢吡咯环以构造具有一定刚性的手性配体骨架,此外引入不同苯并杂环结构,利用不同电负性的杂原子(N、O、S)来调节配体的电子效应。通过调整配体上可变位置的取代基,来调节金属中心的路易斯酸性和空间位阻,期望筛选出集高活性、高选择性于一体的高效催化剂,进一步提高工业化应用潜力。
本发明提供的含手性四氢吡咯骨架氨基酚氧基锌络合物(I),其特征在于,具有以下通式:
式(I)中:
R1~R2分别代表氢,C1~C20直链、支链或环状结构的烷基,C7~C30的单或多芳基取代烷基,卤素;R1~R2也可以分别代表取代硅基SiR3R4R5,其中R3~R5分别为C1~C10直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基,C6~C18的芳基,R3、R4和R5可以相同或不同;
X代表氨基NR6R7,其中R6~R7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,R6和R7可以相同或不同;
A为具有如式(II)、(III)或(IV)所示的基团:
式(II)中,R8代表C1~C20直链、支链或环状结构的烷基,C7~C30的单或多芳基取代烷基,C6~C18的芳基;
A通过其氮原子与锌金属中心配位;
更特征的,式(I)中,R1~R2为氢,C1~C8直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基,卤素;R1~R2代表取代硅基SiR3R4R5时,R3~R5优选为C1~C6直链、支链或环状结构的烷基,C7~C12的单或多芳基取代烷基,C6~C12的芳基;
当A为式(II)时,R8为C1~C8直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基,C6~C12的芳基;
X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)中,R1~R2优选为氢、甲基、异丙基、叔丁基、枯基、三苯甲基、三甲基硅基、三苯基硅基或卤素;R8优选为甲基、乙基、异丙基、正丁基、叔丁基、正己基、正辛基、环戊基、环己基、环辛基、苯基、苄基、苯乙基、二苯甲基、三苯甲基;X优选为二(三甲基硅)氨基。
优选的含手性四氢吡咯骨架氨基酚氧基锌络合物结构为:
本发明的含手性四氢吡咯骨架氨基酚氧基锌络合物(I)制备方法如下所示:
将式(V)所示的含手性四氢吡咯骨架氨基酚类配体化合物与锌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含手性四氢吡咯骨架氨基酚氧基锌目标化合物(I);
上述制备方法中取代基R1、R2和基团A与满足本发明的含手性四氢吡咯骨架氨基酚氧基锌络合物(I)的各相应基团一致;
锌金属原料化合物具有通式ZnX2,X与满足本发明的含手性四氢吡咯骨架氨基酚氧基锌络合物(I)的相应基团一致;
锌金属原料化合物优选为二{二(三甲基硅)氨基}锌;
含手性四氢吡咯骨架氨基酚类配体化合物与锌金属原料化合物的摩尔比为1:1~1.5;
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。
对于式(V)所示的含手性四氢吡咯骨架氨基酚类配体化合物,当A为如式(II)所示的基团时,其结构如式(V-1)所示,合成方法如下:
将手性Boc-脯氨酸与式(VI)所示N-取代邻苯二胺在氯甲酸异丁酯以及N-甲基吗啉存在下反应,再用乙酰氯脱除Boc保护基团生成相应仲胺(VIII)(Tetrahedron:Asymmetry.2017,28,954-963),之后在碱性条件下与式(IX)所示2-溴甲基-4,6-二取代苯酚反应,然后从反应产物中收集式(V-1)所示含手性四氢吡咯骨架氨基酚类配体化合物;
上述制备方法中,式(VI)所示N-取代邻苯二胺的合成可参考文献方法按以下路线由邻苯二胺与氯代烃在甲醇溶液中反应获得(Tetrahedron:Asymmetry.2014,25,1590-1598;Synth Commun.2006,36,1857-1861):
式(IX)所示2-溴甲基-4,6-二取代苯酚的合成可参考文献方法按以下路线由2,4-取代苯酚与多聚甲醛在33%溴化氢的醋酸溶液中反应获得(Inorg.Chem.2002,41,3656-3667;J.Org.Chem.1994,59,1939-1942):
式(V)所示的含手性四氢吡咯骨架氨基酚类配体化合物,当A为如式(III)所示的基团时,其结构如式(V-2)所示,合成方法如下:
将手性Boc-脯氨酸与2-溴苯胺在氯甲酸异丁酯以及N-甲基吗啉存在下反应得到酰胺(X),然后在碱性条件下加入1,10-邻二氮杂菲形成噁唑环、用三氟乙酸脱除Boc保护基生成相应仲胺(XII)(2016,US9321769),之后在碱性条件下与2-溴甲基-4,6-二取代苯酚(IX)反应,然后从反应产物中收集式(V-2)所示含手性四氢吡咯骨架氨基酚类配体化合物;
式(V)所示的含手性四氢吡咯骨架氨基酚类配体化合物,当A为如式(IV)所示的基团时,其结构如式(V-3)所示,合成方法如下:
将手性脯氨酸与邻氨基苯硫酚反应生成相应仲胺(XIII)(Dalton Trans.2013,42,6058-6073),之后在碱性条件下与2-溴甲基-4,6-二取代苯酚(IX)反应,然后从反应产物中收集式(V-3)所示含手性四氢吡咯骨架氨基酚类配体化合物。
本发明所述的含手性四氢吡咯骨架氨基酚氧基锌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、ε-己内酯、β-丁内酯、α-甲基三亚甲基环碳酸酯的聚合反应,聚合方式为溶液聚合和熔融聚合。
以本发明所述的含手性四氢吡咯骨架氨基酚氧基锌络合物为催化剂,催化丙交酯在-40~140℃聚合,优选-20~110℃;聚合时催化剂与单体摩尔比为1:1~10000,优选为1:100~5000。
以本发明所述的含手性四氢吡咯骨架氨基酚氧基锌络合物为催化剂,在加醇的条件下,催化丙交酯在-40~140℃聚合,优选-20~110℃;聚合时催化剂与醇以及单体摩尔比为1:1~50:1~10000,优选为1:1~50:100~5000;所述的醇为C1~C10直链、支链或环状结构的烷基醇,C7~C20的单或多芳基取代烷基醇。
以本发明所述的含手性四氢吡咯骨架氨基酚氧基锌络合物为催化剂,在加醇或不加醇的条件下,使ε-己内酯聚合,聚合时催化剂与醇以及单体摩尔比为1:0~50:1~10000,优选为1:0~50:100~5000;所述的醇为C1~C10直链、支链或环状结构的烷基醇,C7~C20的单或多芳基取代烷基醇。
本发明提供的催化剂原料易得,制备方便、性质稳定,同时具有较高的催化活性及高立体选择性,易获得高立体等规度、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。下面通过实例进一步说明本发明,但本发明不限于此。
具体实施方式
实施例1
配体L1H的合成:
(1)(S)-1-苄基-2-(吡咯烷-2-基)-1H-苯并咪唑的合成
在惰性气体保护下,0℃下依次向三口瓶中加入L-Boc-脯氨酸(8.5g,39mmol)、四氢呋喃(100mL)、等当量N-甲基吗啉(3.7mL,39.3mmol)和氯甲酸异丁酯(5.1mL,39.3mmol),0℃下搅拌几分钟后加入N-苄基邻苯二胺(7.8g,39mmol),缓慢升至室温反应过夜。减压除去溶剂,固体用水溶解,二氯甲烷萃取,有机相依次用NaHCO3溶液和饱和食盐水洗,Na2SO4干燥,过滤,减压除去溶剂。所得固体用冰醋酸溶解,在65℃反应1小时,如上常规处理后,用柱色谱法纯化得到白色固体。0℃下依次向三口瓶中加入该白色固体,甲醇80mL,缓慢加入乙酰氯5mL,将系统加热到60℃反应2小时。减压除去溶剂,所得固体用二氯甲烷溶解,用氨水调pH至9~10,有机相依次用NaHCO3溶液和饱和食盐水洗,Na2SO4干燥,过滤,减压除去溶剂,得到黄色油状物(7.2g,66%,纯度90%)。
(2)配体L1H的合成
向单口瓶中依次加入(S)-1-苄基-2-(吡咯烷-2-基)-1H-苯并咪唑(1.9g,纯度90%,约6.0mmol)、无水碳酸钾(1.3g,9.0mmol)和N,N-二甲基甲酰胺(60mL),搅拌几分钟后加入2-溴甲基-4,6-二叔丁基苯酚(1.8g,6.0mmol),室温反应过夜。加水淬灭,用二氯甲烷萃取,有机相用饱和食盐水洗,无水Na2SO4干燥,过滤,减压除去溶剂。用二氯甲烷和甲醇重结晶,得白色固体L1H(2.2g,75%)。
1H NMR(400MHz,CDCl3):δ10.62(br s,1H),7.84(d,3J=8.0Hz,1H),7.29–7.13(m,7H),6.93–6.84(m,2H),6.53(s,1H),5.09(d,2J=17.2Hz,1H),4.76(d,2J=17.2Hz,1H),4.08(d,2J=13.2Hz,1H),4.00(pseudo-t,3J=6.4Hz,1H),3.38(d,2J=13.2Hz,1H),3.33–3.25(m,1H),2.79–2.66(m,1H),2.20–2.04(m,3H),1.97–1.85(m,1H),1.43(s,9H),1.19(s,9H).13C{1H}NMR(100MHz,CDCl3):δ155.01,154.32,142.62,140.32,136.35,135.65,135.25,129.05,127.93,127.90,126.05,125.97,123.41,123.32,123.16,123.10,122.80,122.77,122.40,121.98,119.98,109.72,58.51,57.03,56.91,53.44,53.37,46.45,46.39,35.06,34.13,31.81,31.73,31.65,29.85,29.78,23.68.Anal.Calcd.for C33H41N3O:C,79.96;H,8.34;N,8.48.Found:C,79.94;H,8.26;N,8.43%.
实施例2
配体L2H的合成
除原料采用(S)-1-苄基-2-(吡咯烷-2-基)-1H-苯并咪唑(1.9g,纯度90%,约6.0mmol)、无水碳酸钾(1.2g,9.0mmol)和2-溴甲基-4,6-二枯基苯酚(2.5g,6.0mmol)外,其他操作同实施例1,得白色固体L2H(2.8g,76%)。
1H NMR(400MHz,CDCl3):δ10.37(br s,1H),7.73(d,3J=7.8Hz,1H),7.30–7.06(m,17H),6.85–6.77(m,2H),6.45(d,4J=2.0Hz,1H),4.94(d,2J=16.8Hz,1H),4.66(d,2J=16.8Hz,1H),3.92(d,2J=13.6Hz,1H),3.89(pseudo-t,3J=7.6Hz,1H),3.24(d,2J=13.6Hz,1H),3.19–3.11(m,1H),2.69–2.60(m,1H),2.10–1.93(m,3H),1.85–1.70(m,1H),1.68(s,3H),1.64(s,3H),1.61(s,3H),1.57(s,3H).13C{1H}NMR(100MHz,CDCl3):δ154.54,153.88,151.47,151.29,142.52,139.72,136.27,135.19,135.10,129.03,128.00,127.90,127.71,126.77,125.95,125.93,125.89,125.79,125.50,125.33,125.27,125.06,125.01,124.94,122.75,122.39,122.10,119.91,109.79,57.96,57.85,56.16,56.07,52.97,52.91,46.50,42.35,42.20,31.27,31.19,30.95,29.78,29.48,23.28.Anal.Calcd.forC43H45N3O:C,83.32;H,7.32;N,6.78.Found:C,83.30;H,7.20;N,6.73%.
实施例3
配体L3H的合成
除原料采用(S)-1-苄基-2-(吡咯烷-2-基)-1H-苯并咪唑(6.8g,纯度90%,约22mmol)、无水碳酸钾(4.6g,33mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(9.8g,22mmol)外,其他操作同实施例1,得白色固体L3H(12g,85%)。
1H NMR(400MHz,CDCl3):δ10.25(br s,1H),7.71(d,3J=8.0Hz,1H),7.30–7.22(m,10H),7.22–7.09(m,11H),6.95(d,4J=1.6Hz,1H),6.85–6.78(m,2H),6.46(d,4J=1.6Hz,1H),4.93(d,2J=17.1Hz,1H),4.68(d,2J=17.1Hz,1H),3.99(d,2J=13.6Hz,1H),3.76(dd,3J=7.6Hz,3J=5.0Hz,1H),3.30(d,2J=13.6Hz,1H),3.15–3.05(m,1H),2.69–2.58(m,1H),2.12(s,3H),2.08–1.86(m,3H),1.81–1.69(m,1H).13C{1H}NMR(100MHz,CDCl3):δ154.10,154.02,146.16,142.56,136.03,135.14,133.95,131.21,130.64,130.55,129.03,128.39,128.31,127.94,127.92,127.06,126.61,126.10,126.01,125.39,123.10,122.76,122.35,119.90,109.90,63.40,57.49,57.37,55.06,54.92,52.09,52.05,46.74,30.93,22.97,21.01,20.95.Anal.Calcd.for C45H41N3O:C,84.47;H,6.46;N,6.57.Found:C,84.42;H,6.47;N,6.43%.
实施例4
配体L4H的合成:
(1)(S)-1-正己基-2-(吡咯烷-2-基)-1H-苯并咪唑的合成
除原料采用L-Boc-脯氨酸(15g,71mmol)、N-甲基吗啉(7.8mL,71mmol)、氯甲酸异丁酯(9.2mL,71mmol)和N-正己基邻苯二胺(14g,71mmol)外,其他操作同实施例1,得到黄色油状物(8.2g,纯度80%,73%)。
(2)配体L4H的合成
除原料采用(S)-1-正己基-2-(吡咯烷-2-基)-1H-苯并咪唑(5.9g,纯度80%,约17mmol)、无水碳酸钾(3.6g,26mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(7.7g,17mmol)外,其他操作同实施例1,得白色固体L4H(6.1g,56%)。
1H NMR(400MHz,CDCl3):δ10.32(br s,1H),7.72–7.65(m,1H),7.30–7.19(m,15H),7.15(t,3J=6.9Hz,3H),6.90(d,4J=1.2Hz,1H),6.38(d,4J=1.2Hz,1H),3.93(d,2J=13.3Hz,1H),3.83(dd,3J=8.0Hz,3J=4.5Hz,1H),3.77(ddd,2J=14.8Hz,3J=8.4Hz,3J=6.0Hz,1H),3.54–3.46(m,1H),3.28(d,2J=13.3Hz,1H),3.15–3.06(m,1H),2.68–2.59(m,1H),2.18–1.95(m,3H),2.07(s,3H),1.85–1.75(m,1H),1.66–1.48(m,2H),1.31–1.12(m,6H),0.85(t,3J=6.8Hz,3H).13C{1H}NMR(100MHz,CDCl3):δ154.05,153.79,146.25,142.57,134.74,133.80,131.21,130.65,130.52,128.35,128.24,127.06,126.53,125.41,123.08,122.38,122.34,122.08,122.02,119.85,109.64,109.60,63.39,56.96,56.78,54.83,54.66,52.01,51.94,43.55,31.48,31.25,30.04,26.70,23.09,22.64,20.95,20.89,14.12,14.03.Anal.Calcd.for C44H47N3O:C,83.37;H,7.47;N,6.63.Found:C,83.59;H,7.50;N,6.43%.
实施例5
配体L5H合成
(1)(S)-1-苯基-2-(吡咯烷-2-基)-1H-苯并咪唑的合成
除原料采用L-Boc-脯氨酸(13g,60mmol)、N-甲基吗啉(6.6mL,60mmol)、氯甲酸异丁酯(7.8mL,60mmol)和N-苯基邻苯二胺(11g,60mmol)外,其他操作同实施例1,得到黄色油状物(9.5g,纯度90%,60%)。
(2)配体L5H的合成
除原料采用(S)-1-苯基-2-(吡咯烷-2-基)-1H-苯并咪唑(4.9g,纯度90%,约17mmol)、无水碳酸钾(3.5g,25mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(7.4g,17mmol)外,其他操作同实施例1,得白色固体L5H(8.3g,80%)。
1H NMR(400MHz,CDCl3):δ10.20(br s,1H),7.76(d,3J=8.0Hz,1H),7.50(br s,3H),7.29(t,3J=8.0Hz,1H),7.26–7.05(m,18H),7.02(d,3J=8.0Hz,1H),6.84(d,4J=1.2Hz,1H),6.51(d,4J=1.2Hz,1H),3.90–3.80(m,2H),3.42(d,2J=13.3Hz,1H),3.17–3.08(m,1H),2.59–2.51(m,1H),2.10(s,3H),2.04–1.93(m,3H),1.76–1.64(m,1H).13C{1H}NMR(100MHz,CDCl3):δ154.16,154.05,146.19,142.49,136.44,135.52,133.85,131.14,130.64,130.54,129.99,129.19,128.23,128.14,127.78,127.73,126.99,126.37,125.32,123.10,123.00,122.66,119.83,110.32,110.27,63.24,57.35,57.21,54.81,54.75,51.57,51.49,31.49,22.83,21.00,20.94.Anal.Calcd.for C44H39N3O:C,84.45;H,6.28;N,6.71.Found:C,84.17;H,6.31;N,6.66%.
实施例6
配体L6H的合成
(1)(S)-1-甲基-2-(吡咯烷-2-基)-1H-苯并咪唑的合成
除原料采用L-Boc-脯氨酸(11g,51mmol)、N-甲基吗啉(5.6mL,51mmol)、氯甲酸异丁酯(6.6mL,51mmol)和N-甲基邻苯二胺(6.2g,51mmol)外,其他操作同实施例1,得到黄色油状物(6.1g,纯度90%,60%)。
(2)配体L6H的合成
除原料采用(S)-1-甲基-2-(吡咯烷-2-基)-1H-苯并咪唑(2.5g,纯度90%,约11mmol)、无水碳酸钾(2.3g,17mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(5.0g,11mmol)外,其他操作同实施例1,得白色固体L6H(4.9g,76%)。
1H NMR(400MHz,CDCl3):δ10.27(br s,1H),7.70–7.65(m,1H),7.32–7.17(m,15H),7.14(t,3J=7.2Hz,3H),6.93(d,4J=1.6Hz,1H),6.35(d,4J=1.6Hz,1H),3.95(d,2J=13.6Hz,1H),3.75(dd,3J=8.0Hz,3J=4.8Hz,1H),3.24(d,2J=13.6Hz,1H),3.12(s,3H),3.07–2.95(m,1H),2.66–2.57(m,1H),2.18–2.09(m,1H),2.08(s,3H),2.08–1.93(m,2H),1.88–1.76(m,1H).13C{1H}NMR(100MHz,CDCl3):δ153.84,153.52,146.15,142.26,135.72,133.79,131.17,130.51,130.44,128.20,128.15,127.04,126.70,125.38,122.88,122.52,122.12,119.68,109.21,63.43,57.75,57.64,55.23,55.12,52.42,30.62,29.71,29.69,23.16,20.88,20.84.Anal.Calcd.for C39H37N3O:C,83.09;H,6.62;N,7.45.Found:C,83.31;H,6.39;N,7.32%.
实施例7
配体L7H的合成:
(1)(R)-1-甲基-2-(吡咯烷-2-基)-1H-苯并咪唑的合成
除原料采用D-Boc-脯氨酸(13g,60mmol)、N-甲基吗啉(6.6mL,60mmol)、氯甲酸异丁酯(7.8mL,60mmol)和N-甲基邻苯二胺(7.3g,60mmol)外,其他操作同实施例1,得到黄色油状物(8.0g,纯度90%,66%)。
(2)配体L7H的合成
除原料采用(R)-1-甲基-2-(吡咯烷-2-基)-1H-苯并咪唑(3.2g,纯度90%,约14mmol)、无水碳酸钾(2.9g,21mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(6.3g,14mmol)外,其他操作同实施例1,得白色固体L7H(6.2g,78%)。
1H NMR(400MHz,CDCl3):δ10.27(br s,1H),7.70–7.65(m,1H),7.32–7.17(m,15H),7.14(t,3J=7.2Hz,3H),6.93(d,4J=1.6Hz,1H),6.35(d,4J=1.6Hz,1H),3.95(d,2J=13.2Hz,1H),3.75(dd,3J=7.6Hz,3J=4.8Hz,1H),3.24(d,2J=13.6Hz,1H),3.12(s,3H),3.07–2.95(m,1H),2.66–2.57(m,1H),2.18–2.09(m,1H),2.08(s,3H),2.08–1.93(m,2H),1.88–1.76(m,1H).13C{1H}NMR(100MHz,CDCl3):δ153.84,153.55,146.17,142.28,135.74,133.81,131.19,130.56,130.43,128.24,128.13,127.06,126.71,125.36,122.90,122.53,122.13,119.69,109.20,63.45,57.85,57.67,55.30,55.13,52.44,52.40,30.63,29.73,29.68,23.16,20.89,20.83.Anal.Calcd.for C39H37N3O:C,83.09;H,6.62;N,7.45.Found:C,82.86;H,6.68;N,7.39%.
实施例8
配体L8H的合成
(1)(S)-2-(吡咯烷-2-基)-苯并噁唑的合成
在惰性气体保护下,依次向三口瓶中加入L-Boc-脯氨酸(13g,60mmol)、二氯甲烷(100mL)、等当量的N-甲基吗啉(6.6mL,60mmol)和氯甲酸异丁酯(7.8mL,60mmol),0℃下搅拌1小时。再向体系中加入2-溴苯胺(10g,60mmol),缓慢升至室温反应过夜。加水淬灭,二氯甲烷萃取,Na2SO4干燥,过滤,减压除去溶剂。用柱色谱法纯化,得到淡黄色油状物。在惰性气体保护下,将上述淡黄色油状物用乙二醇二甲醚(100mL)溶解后加入三口瓶中,再依次加入CuI(1.1g,6.0mmol),Cs2CO3(20g,60mmol)和1,10-邻二氮杂菲(3.6g,20mmol),将反应混合物加热到85℃反应过夜。硅藻土过滤,减压除去溶剂。用柱色谱法纯化,得到白色固体。在惰性气体保护下,0℃下依次向三口瓶中加入上述白色固体,二氯甲烷(100mL)和三氟乙酸(40mL),室温反应3小时。用氨水调pH至9~10,二氯甲烷萃取,Na2SO4干燥,过滤,减压除去溶剂,得到淡黄色油状产物(9.1g,纯度90%,81%)。
(2)配体L8H的合成
除原料采用(S)-2-(吡咯烷-2-基)-苯并噁唑(5.3g,纯度90%,约25mmol)、无水碳酸钾(5.3g,38mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(11g,25mmol)外,其他操作同实施例1,得白色固体L8H(12g,84%)。
1H NMR(400MHz,CDCl3):δ9.79(s,1H),7.71–7.64(m,1H),7.47–7.41(m,1H),7.36–7.29(m,2H),7.30–7.23(m,12H),7.22–7.13(m,3H),6.86(s,1H),6.67(s,1H),3.94(dd,3J=7.6Hz,3J=6.0Hz,1H),3.90(d,2J=13.6Hz,1H),3.54(d,2J=13.6Hz,1H),2.82–2.73(m,1H),2.48–2.39(m,1H),2.23–2.06(m,2H),2.12(s,3H),1.96–1.84(m,1H),1.83–1.71(m,1H).13C{1H}NMR(100MHz,CDCl3):δ165.57,153.64,150.76,146.14,140.89,134.03,131.19,130.80,130.72,128.38,128.31,127.06,126.79,125.42,125.15,124.45,122.49,120.10,110.94,63.33,60.57,60.45,56.03,51.70,29.91,22.71,21.03,20.98.Anal.Calcd.for C38H34N2O2:C,82.88;H,6.22;N,5.09.Found:C,82.79;H,6.10;N,4.87%.
实施例9
配体L9H的合成
(1)(S)-2-(吡咯烷-2-基)-苯并噻唑的合成
在惰性气体保护下,室温下依次向三口瓶中加入L-脯氨酸(6.8g,59mmol),邻氨基苯硫酚(7.3g,59mmol),多聚磷酸40g,反应体系升至220℃反应4小时,得棕色油状物。将上述油状物倒入5mol/L的NaOH溶液中,二氯甲烷萃取,有机相用0.1mol/L的盐酸洗涤,水相用5mol/L的NaOH溶液调pH至9~10,二氯甲烷萃取,合并有机相,Na2SO4干燥,过滤,减压除去溶剂,得到黄色油状产物(8.5g,纯度90%,71%)。
(2)配体L9H的合成
除原料采用(S)-2-(吡咯烷-2-基)-苯并噻唑(4.8g,纯度90%,约21mmol)、无水碳酸钾(4.4g,32mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(9.5g,21mmol)外,其他操作同实施例1,得黄色固体L9H(8.2g,68%)。
1H NMR(400MHz,CDCl3):δ9.16(s,1H),7.92(d,3J=8.0Hz,1H),7.82(d,3J=7.1Hz,1H),7.45(pseudo-t,3J=7.8Hz,1H),7.36(pseudo-t,3J=7.8Hz,1H),7.29–7.22(m,12H),7.21–7.14(m,3H),6.86(s,1H),6.74(s,1H),4.09(d,2J=13.3Hz,1H),4.01(dd,3J=8.3Hz,3J=6.9Hz,1H),3.42(d,2J=13.3Hz,1H),2.82–2.74(m,1H),2.39–2.28(m,2H),2.13(s,3H),2.02–1.91(m,1H),1.84–1.72(m,2H).13C{1H}NMR(100MHz,CDCl3):δ174.51,153.33,153.12,146.12,135.15,134.06,131.25,130.87,130.76,128.69,128.59,127.10,127.01,126.05,125.47,125.11,122.95,122.80,121.99,66.85,66.70,63.38,57.38,57.27,52.93,33.30,22.74,21.04,20.97.Anal.Calcd.for C38H34N2OS:C,80.53;H,6.05;N,4.94.Found:C,80.55;H,6.10;N,4.79%.
实施例10
络合物Zn1的合成
在手套箱里,将Zn[N(SiMe3)2]2(0.31g,0.79mmol)加入50mL Schlenk瓶,用5mL甲苯溶解,配体L1H(0.39g,0.79mmol)先溶于5mL甲苯,然后缓慢加入上述反应体系,室温反应过夜。过滤除去不溶性杂质,真空减压抽除溶剂和自由硅胺,得淡黄色泡状固体,用甲苯和正己烷重结晶,得无色晶体(0.42g,74%)。
1H NMR(400MHz,C6D6):δ7.79(d,3J=8.0Hz,1H),7.20(d,4J=2.6Hz,1H),6.97–6.88(m,4H),6.74(d,4J=2.6Hz,1H),6.70(t,3J=7.8Hz,1H),6.38–6.35(m,3H),4.52(d,2J=11.6Hz,1H),4.46(d,2J=16.4Hz,1H),4.30(d,2J=16.4Hz,1H),3.74–3.63(m,2H),2.75(d,2J=11.6Hz,1H),2.24–2.14(m,1H),1.89–1.77(m,1H),1.46(s,9H),1.35(s,9H),1.31–1.24(m,2H),1.19–1.09(m,1H),0.61(s,18H).13C{1H}NMR(100MHz,C6D6):δ164.71,156.99,138.93,137.89,135.26,134.71,133.74,129.48,129.35,126.47,126.38,124.63,124.51,124.23,124.14,122.27,119.71,110.61,110.52,63.51,60.59,60.46,56.96,56.85,47.12,35.55,34.07,32.52,32.42,32.31,30.19,30.09,24.84,6.59,6.54.Anal.Calcd.for C39H58N4OSi2Zn:C,65.02;H,8.11;N,7.78.Found:C,64.94;H,8.26;N,7.79%.
实施例11
络合物Zn2的合成
除原料采用Zn[N(SiMe3)2]2(0.32g,0.84mmol)和配体L2H(0.52g,0.84mmol)外,其他操作同实施例10,得无色晶体(0.51g,72%)。
1H NMR(400MHz,C6D6):δ7.81(d,3J=8.3Hz,1H),7.27(d,3J=8.3Hz,2H),7.22–7.13(m,6H),7.09–7.01(m,3H),6.99(d,4J=2.5Hz,1H),6.96–6.85(m,4H),6.60(d,3J=8.0Hz,1H),6.53(d,4J=2.5Hz,1H),6.44(d,3J=6.4Hz,2H),4.45(d,2J=16.8Hz,1H),4.26(d,2J=11.6Hz,1H),4.16(d,2J=16.8Hz,1H),3.52(ddd,2J=10.0Hz,3J=6.4Hz,3J=4.0Hz,1H),3.43(dd,3J=9.0Hz,3J=6.5Hz,1H),2.50(d,2J=11.6Hz,1H),1.96(td,2J=9.2Hz,3J=6.0Hz,1H),1.87–1.74(m,1H),1.80(s,3H),1.64(s,3H),1.63(s,3H),1.54(s,3H),1.20–1.03(m,3H),0.50(s,18H).13C{1H}NMR(100MHz,C6D6):δ164.65,157.12,152.91,152.53,138.34,137.87,135.35,134.91,132.68,129.30,127.34,126.90,126.67,126.46,126.36,125.40,124.86,124.11,122.80,119.99,119.96,110.52,110.38,62.73,60.55,60.51,56.66,56.58,46.86,43.36,42.18,32.26,31.67,31.58,27.77,27.74,24.59,6.50,6.47.Anal.Calcd.for C49H62N4OSi2Zn:C,69.68;H,7.40;N,6.63.Found:C,69.69;H,7.54;N,6.56%.
实施例12
络合物Zn3的合成
除原料采用Zn[N(SiMe3)2]2(0.32g,0.84mmol)和配体L3H(0.54g,0.84mmol)外,其他操作同实施例10,得淡黄色晶体(0.52g,71%)。
1H NMR(400MHz,C6D6):δ7.48(d,3J=7.6Hz,6H),7.34(d,3J=8.0Hz,1H),7.29(d,4J=1.5Hz,1H),7.00(t,3J=8.0Hz,1H),6.98–6.88(m,9H),6.87–6.78(m,4H),6.49(d,4J=1.5Hz,1H),6.47(d,3J=8.3Hz,1H),6.25(d,3J=7.2Hz,2H),4.47(d,2J=11.6Hz,1H),4.14(s,2H),3.90(dd,3J=6.0Hz,3J=5.7Hz,1H),3.64(dt,2J=11.2Hz,3J=6.0Hz,1H),2.85(d,2J=11.6Hz,1H),2.33–2.24(m,1H),2.11(s,3H),1.58–1.46(m,2H),1.35–1.25(m,1H),1.10–0.99(m,1H),0.33(s,18H).13C{1H}NMR(100MHz,C6D6):δ165.63,156.48,147.75,137.52,136.34,135.19,134.01,133.81,133.73,131.75,131.71,130.91,130.80,129.50,126.91,126.07,126.02,125.32,124.03,121.92,121.15,121.10,119.60,110.41,64.15,63.16,59.61,59.44,57.16,46.89,32.40,24.60,21.22,21.17,6.54.Anal.Calcd.forC51H58N4OSi2Zn:C,70.85;H,6.76;N,6.48.Found:C,70.70;H,6.80;N,6.32%.
实施例13
络合物Zn4的合成
除原料采用Zn[N(SiMe3)2]2(0.32g,0.84mmol)和配体L4H(0.53g,0.84mmol)外,其他操作同实施例10,得淡黄色晶体(0.31g,43%)。
1H NMR(400MHz,C6D6):δ7.43(d,3J=7.3Hz,6H),7.37–7.32(m,2H),7.01–6.95(m,8H),6.89(t,3J=7.2Hz,3H),6.64(d,3J=8.0Hz,1H),6.52(d,4J=2.0Hz,1H),4.43(d,2J=11.6Hz,1H),3.86(dd,3J=8.8Hz,3J=5.2Hz,1H),3.68–3.60(dt,2J=11.0Hz,3J=5.5Hz,1H),3.19–3.08(m,1H),3.01–2.91(m,1H),2.82(d,2J=11.6Hz,1H),2.30–2.20(m,1H),2.11(s,3H),1.68–1.54(m,2H),1.32(dt,2J=10.4Hz,4J=4.8Hz,1H),1.18–1.08(m,3H),1.07–0.95(m,4H),0.83(t,3J=7.2Hz,3H),0.78–0.64(m,2H),0.35(s,18H).13C{1H}NMR(100MHz,C6D6):δ165.81,156.30,147.77,137.55,136.01,135.19,133.64,131.74,131.68,130.50,126.92,125.24,123.80,121.85,121.18,119.24,109.85,64.15,62.89,59.72,59.54,57.16,57.07,43.60,32.25,31.38,29.06,26.27,24.53,22.63,21.13,21.07,14.23,6.54.Anal.Calcd.for C50H64N4OSi2Zn:C,69.94;H,7.51;N,6.53.Found:C,69.88;H,7.61;N,6.27%.
实施例14
络合物Zn5的合成
除原料采用Zn[N(SiMe3)2]2(0.32mg,0.84mmol)和配体L5H(0.53g,0.84mmol)外,其他操作同实施例10,得淡黄色晶体(0.58g,80%)。
1H NMR(400MHz,C6D6):δ7.49(d,3J=7.5Hz,6H),7.38(d,3J=8.0Hz,1H),7.18(d,4J=2.0Hz,1H),7.08–6.95(m,10H),6.92(t,3J=7.2Hz,3H),6.86(t,3J=7.4Hz,1H),6.56(brs,2H),6.49(d,3J=8.3Hz,1H),6.40(d,4J=2.0Hz,1H),4.32(d,2J=11.6Hz,1H),3.75(dd,3J=9.6Hz,3J=5.6Hz,1H),3.59–3.51(m,1H),2.59(d,2J=11.6Hz,1H),2.13(s,3H),2.11–2.02(m,1H),1.76–1.63(m,1H),1.37–1.26(m,1H),1.25–1.11(m,2H),0.39(s,18H).13C{1H}NMR(100MHz,C6D6):δ166.08,157.06,147.86,137.36,136.63,135.69,134.13,133.66,133.56,131.73,130.24,130.17,127.09,127.03,125.19,122.02,120.66,120.61,119.14,110.24,64.24,62.37,60.29,60.15,56.84,32.53,24.36,21.06,21.00,6.52.Anal.Calcd.for C50H56N4OSi2Zn:C,70.61;H,6.64;N,6.59.Found:C,70.63;H,6.75;N,6.47%.
实施例15
络合物Zn6的合成
除原料采用Zn[N(SiMe3)2]2(0.39g,1.0mmol)和配体L6H(0.56g,1.0mmol),重结晶溶剂用四氢呋喃和正己烷外,其他操作同实施例10,得淡黄色晶体(0.55g,70%)。
1H NMR(400MHz,C6D6):δ7.51(d,3J=7.8Hz,6H),7.32(d,3J=8.0Hz,1H),7.22(d,4J=2.0Hz,1H),7.09–6.98(m,7H),6.97–6.89(m,4H),6.60(d,4J=2.0Hz,1H),6.36(d,3J=8.0Hz,1H),4.44(d,2J=12.0Hz,1H),3.75(dd,3J=8.5Hz,3J=5.0Hz,1H),3.67–3.59(m,1H),2.89(d,2J=12.0Hz,1H),2.34–2.24(m,1H),2.11(s,3H),2.03(s,3H),1.59–1.44(m,2H),1.36–1.27(m,1H),0.98–0.88(m,1H),0.31(s,18H).13C{1H}NMR(100MHz,C6D6):δ166.10,156.21,147.83,137.17,136.03,135.70,133.81,133.75,131.81,130.50,130.43,127.10,125.21,123.70,121.94,121.04,119.64,109.53,109.48,64.23,63.13,59.39,59.29,57.19,31.58,28.82,28.78,24.46,21.15,21.11,6.51.Anal.Calcd.forC45H54N4OSi2Zn:C,68.55;H,6.90;N,7.11.Found:C,67.91;H,6.84;N,6.95%.
实施例16
络合物Zn7的合成
除原料采用Zn[N(SiMe3)2]2(0.32g,0.82mmol)和配体L7H(0.46g,0.82mmol)外,其他操作同实施例10,得淡黄色晶体(0.40g,61%)。
1H NMR(400MHz,C6D6):δ7.51(d,3J=7.8Hz,6H),7.32(d,3J=8.0Hz,1H),7.22(d,4J=2.0Hz,1H),7.06(t,3J=8.0Hz,1H),7.09–6.98(m,7H),6.97–6.89(m,4H),6.60(d,4J=2.0Hz,1H),6.36(d,3J=8.0Hz,1H),4.44(d,2J=12.0Hz,1H),3.75(dd,3J=8.5Hz,3J=5.0Hz,1H),3.67–3.59(m,1H),2.89(d,2J=12.0Hz,1H),2.34–2.24(m,1H),2.11(s,3H),2.03(s,3H),1.59–1.44(m,2H),1.36–1.27(m,1H),0.98–0.88(m,1H),0.31(s,18H).13C{1H}NMR(100MHz,C6D6):δ166.10,156.21,147.83,137.16,136.02,135.70,133.83,133.72,131.83,131.79,130.56,130.39,127.16,127.00,125.21,123.73,121.95,121.06,120.97,119.64,109.57,109.44,64.23,63.15,59.43,59.24,57.20,31.59,28.82,28.78,24.46,21.16,21.10,6.51.Anal.Calcd.for C45H54N4OSi2Zn:C,68.55;H,6.90;N,7.11.Found:C,68.41;H,7.02;N,7.18%.
实施例17
络合物Zn8的合成
除原料采用Zn[N(SiMe3)2]2(0.32g,0.82mmol)和配体L8H(0.45g,0.82mmol)外,其他操作同实施例10,得淡黄色固体(0.34g,54%)。
1H NMR(400MHz,C6D6):δ7.50(d,3J=7.6Hz,6H),7.30(d,4J=2.4Hz,1H),7.24(d,3J=8.0Hz,1H),7.12–7.02(m,2H×0.60,toluene),6.98(t,3J=7.6Hz,6H),6.89(t,3J=7.6Hz,1H),6.84(t,3J=7.6Hz,3H),6.76(t,3J=8.0Hz,1H),6.71(d,3J=8.0Hz,1H),6.61(d,4J=2.4Hz,1H),4.39(d,2J=12.0Hz,1H),4.05(dd,3J=9.3Hz,3J=3.8Hz,1H),3.50–3.42(m,1H),2.81(d,2J=12.0Hz,1H),2.14(s,3H),2.10(s,3H×0.60,toluene),1.57–1.47(m,1H),1.44–1.32(m,2H),1.29–1.17(m,2H),0.24(s,18H).13C{1H}NMR(100MHz,C6D6):δ170.22,164.92,151.40,147.73,137.89,136.61,135.67,133.83,133.72,131.80,131.76,131.20,127.14,126.97,125.32,125.12,121.48,120.54,110.96,64.11,62.79,59.64,59.43,56.89,29.69,24.61,21.07,20.99,6.37,6.35.Anal.Calcd.forC44H51N3O2Si2Zn·0.60C7H8:C,69.69;H,6.77;N,5.06.Found:C,69.42;H,6.56;N,4.91%.
实施例18
络合物Zn9的合成
除原料采用Zn[N(SiMe3)2]2(0.39g,1.0mmol)和配体L9H(0.57g,1.0mmol),反应溶剂用四氢呋喃外,其他操作同实施例10,得淡黄色晶体(0.54g,68%)。
1H NMR(400MHz,C6D6):δ7.60(d,3J=8.3Hz,1H),7.44(d,3J=7.2Hz,6H),7.30(d,4J=2.3Hz,1H),7.03(t,3J=8.0Hz,1H),6.99(d,3J=8.0Hz,1H),6.89(t,3J=7.6Hz,6H),6.86(t,3J=8.0Hz,1H),6.68–6.59(m,4H),4.49(d,2J=12.4Hz,1H),4.25(dd,3J=8.3Hz,3J=2.8Hz,1H),3.39–3.30(m,1H),2.88(d,2J=12.4Hz,1H),2.25–2.15(m,1H),2.20(s,3H),1.54–1.38(m,1H),1.32–1.22(m,2H),1.19–1.10(m,1H),0.21(s,18H).13C{1H}NMR(100MHz,C6D6):δ177.73,164.46,148.04,147.82,137.66,134.11,134.05,133.98,131.72,131.68,127.03,126.92,125.06,124.95,124.39,121.67,120.20,64.13,63.40,63.26,56.47,56.39,31.85,24.38,21.07,21.00,6.22.Anal.Calcd.for C44H51N3OSSi2Zn:C,66.77;H,6.49;N,5.31.Found:C,66.64;H,6.54;N,5.35%.
实施例19
氩气保护下,在聚合瓶中加入外消旋丙交酯(144mg,1.0mmol),用0.5mL甲苯溶解,取催化剂Zn3的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.002M,[Zn]0:[rac-LA]0=1:500。控制反应温度25℃,反应204分钟,加入石油醚终止反应。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。真空干燥24h。转化率:89%,Mw=4.02×105g/mol,分子量分布PDI=1.39,等规度Pm=0.83。
实施例20
除催化剂换成Zn4外,其他操作同实施实例19。反应194分钟后,转化率:87%,Mw=3.76×105g/mol,分子量分布PDI=1.29,等规度Pm=0.83。
实施例21
除催化剂换成Zn5外,其他操作同实施实例19。反应314分钟后,转化率:82%,Mw=4.06×105g/mol,分子量分布PDI=1.38,等规度Pm=0.81。
实施例22
除催化剂换成Zn6外,其他操作同实施实例19。反应207分钟后,转化率:87%,Mw=3.79×105g/mol,分子量分布PDI=1.37,等规度Pm=0.84。
实施例23
除催化剂换成Zn7外,其他操作同实施实例19。反应203分钟后,转化率:81%,Mw=3.80×105g/mol,分子量分布PDI=1.41,等规度Pm=0.84。
实施例24
除催化剂换成Zn8外,其他操作同实施实例19。反应80分钟后,转化率:86%,Mw=4.09×105g/mol,分子量分布PDI=1.37,等规度Pm=0.78。
实施例25
除催化剂换成Zn9外,其他操作同实施实例19。反应103分钟后,转化率:86%,Mw=3.05×105g/mol,分子量分布PDI=1.40,等规度Pm=0.82。
实施例26
除催化剂换成Zn1、溶剂换成四氢呋喃外,其他操作同实施实例19。反应11分钟后,转化率:91%,Mw=1.54×105g/mol,分子量分布PDI=1.59,等规度Pm=0.65。
实施例27
除催化剂换成Zn2、溶剂换成四氢呋喃外,其他操作同实施实例19。反应20分钟后,转化率:88%,Mw=2.68×105g/mol,分子量分布PDI=1.55,等规度Pm=0.70。
实施例28
除催化剂换成Zn3、溶剂换成四氢呋喃外,其他操作同实施实例19。反应146分钟后,转化率:88%,Mw=2.53×105g/mol,分子量分布PDI=1.45,等规度Pm=0.87。
实施例29
除催化剂换成Zn4、溶剂换成四氢呋喃外,其他操作同实施实例19。反应117分钟后,转化率:81%,Mw=2.55×105g/mol,分子量分布PDI=1.26,等规度Pm=0.86。
实施例30
除催化剂换成Zn5、溶剂换成四氢呋喃外,其他操作同实施实例19。反应109分钟后,转化率:87%,Mw=2.28×105g/mol,分子量分布PDI=1.42,等规度Pm=0.84。
实施例31
除催化剂换成Zn6、溶剂换成四氢呋喃外,其他操作同实施实例19。反应110分钟后,转化率:89%,Mw=2.28×105g/mol,分子量分布PDI=1.46,等规度Pm=0.87。
实施例32
除催化剂换成Zn7、溶剂换成四氢呋喃外,其他操作同实施实例19。反应115分钟后,转化率:86%,Mw=2.31×105g/mol,分子量分布PDI=1.37,等规度Pm=0.87。
实施例33
除催化剂换成Zn8、溶剂换成四氢呋喃外,其他操作同实施实例19。反应34分钟后,转化率:87%,Mw=1.65×105g/mol,分子量分布PDI=1.28,等规度Pm=0.75。
实施例34
除催化剂换成Zn9、溶剂换成四氢呋喃外,其他操作同实施实例19。反应34分钟后,转化率:91%,Mw=1.74×105g/mol,分子量分布PDI=1.43,等规度Pm=0.78。
实施例35
氩气保护下,在聚合瓶中加入外消旋丙交酯(144mg,1.0mmol),用0.5mL异丙醇的甲苯溶液溶解。取催化剂Zn3的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.002M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:500,控制反应温度25℃。反应118分钟,加入石油醚终止反应,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,真空干燥24h。转化率:92%,Mw=1.30×105g/mol,分子量分布PDI=1.21,等规度Pm=0.84。
实施例36
除催化剂换成Zn4外,其他操作同实施实例35。反应133分钟后,转化率:87%,Mw=1.80×105g/mol,分子量分布PDI=1.27,等规度Pm=0.85。
实施例37
除催化剂换成Zn5外,其他操作同实施实例35。反应95分钟后,转化率:91%,Mw=1.23×105g/mol,分子量分布PDI=1.20,等规度Pm=0.83。
实施例38
除催化剂换成Zn6外,其他操作同实施实例35。反应95分钟后,转化率:90%,Mw=1.14×105g/mol,分子量分布PDI=1.16,等规度Pm=0.86。
实施例39
除温度换成–20℃外,其他操作同实施实例38。反应43小时后,转化率:86%,Mw=1.28×105g/mol,分子量分布PDI=1.21,等规度Pm=0.90。
实施例40
除催化剂换成Zn7外,其他操作同实施实例35。反应90分钟后,转化率:90%,Mw=1.16×106g/mol,分子量分布PDI=1.19,等规度Pm=0.85。
实施例41
除催化剂换成Zn8外,其他操作同实施实例35。反应32分钟后,转化率:95%,Mw=1.00×105g/mol,分子量分布PDI=1.26,等规度Pm=0.76。
实施例42
除催化剂换成Zn9外,其他操作同实施实例35。反应36分钟后,转化率:95%,Mw=1.14×105g/mol,分子量分布PDI=1.21,等规度Pm=0.81。
实施例43
除催化剂换成Zn3、溶剂换成四氢呋喃外,其他操作同实施实例35。反应157分钟后,转化率:91%,Mw=8.81×104g/mol,分子量分布PDI=1.27,等规度Pm=0.85。
实施例44
除催化剂换成Zn4、溶剂换成四氢呋喃外,其他操作同实施实例35。反应166分钟后,转化率:83%,Mw=8.76×104g/mol,分子量分布PDI=1.15,等规度Pm=0.83。
实施例45
除催化剂换成Zn5、溶剂换成四氢呋喃外,其他操作同实施实例35。反应140分钟后,转化率:81%,Mw=7.27×104g/mol,分子量分布PDI=1.19,等规度Pm=0.84。
实施例46
除催化剂换成Zn6、溶剂换成四氢呋喃外,其他操作同实施实例35。反应137分钟后,转化率:95%,Mw=1.18×105g/mol,分子量分布PDI=1.25,等规度Pm=0.86。
实施例47
除催化剂换成Zn7、溶剂换成四氢呋喃外,其他操作同实施实例35。反应128分钟后,转化率:92%,Mw=1.02×105g/mol,分子量分布PDI=1.28,等规度Pm=0.85。
实施例48
除催化剂换成Zn8、溶剂换成四氢呋喃外,其他操作同实施实例35。反应50分钟后,转化率:94%,Mw=1.13×105g/mol,分子量分布PDI=1.20,等规度Pm=0.78。
实施例49
除催化剂换成Zn9、溶剂换成四氢呋喃外,其他操作同实施实例35。反应46分钟后,转化率:91%,Mw=1.03×105g/mol,分子量分布PDI=1.23,等规度Pm=0.80。
实施例50
于10mL聚合瓶中加入外消旋丙交酯(288mg,2.0mmol),加入0.1mL的异丙醇/甲苯溶液,再加入0.1mL催化剂Zn6的甲苯溶液。保持[rac-LA]0/[Zn]0/[iPrOH]=5000:1:1。置于110±1°С油浴中搅拌,反应4min,加入石油醚终止聚合。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。真空干燥24h。转化率:92%,Mw=8.35×105g/mol,分子量分布PDI=1.24,等规度Pm=0.75。
实施例51
除[rac-LA]0/[Zn]0/[iPrOH]=5000:1:50外,其他操作同实施实例50。反应4.5min后,转化率:95%,Mw=2.27×105g/mol,分子量分布PDI=1.29,等规度Pm=0.78。
实施例52
除催化剂换成Zn4外,聚合单体换成L-LA外,其他操作同实施实例35。反应3min后,转化率:93%,Mw=2.51×105g/mol,分子量分布PDI=1.30,等规度Pm=1。
实施例53
除催化剂换成Zn4外,聚合单体换成D-LA外,其他操作同实施实例35。反应120min后,转化率:77%,Mw=9.70×104g/mol,分子量分布PDI=1.09,等规度Pm=1。
实施例54
除聚合单体换成ε-己内酯外,其他操作同实施实例35。反应30min后,转化率:90%,Mw=1.42×105g/mol,分子量分布PDI=1.20。
Claims (10)
1.一种含手性四氢吡咯骨架氨基酚氧基锌络合物(I),其特征在于,具有以下通式:
式(I)中:
R1~R2分别代表氢,C1~C20直链、支链或环状结构的烷基,C7~C30的单或多芳基取代烷基,卤素;R1~R2也可以分别代表取代硅基SiR3R4R5,其中R3~R5分别为C1~C10直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基,C6~C18的芳基,R3、R4和R5可以相同或不同;
X代表氨基NR6R7,其中R6~R7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,R6和R7可以相同或不同;
A为具有如式(II)、(III)或(IV)所示的基团:
式(II)中,R8代表C1~C20直链、支链或环状结构的烷基,C7~C30的单或多芳基取代烷基,C6~C18的芳基;
A通过其氮原子与锌金属中心配位。
2.根据权利要求1所述的含手性四氢吡咯骨架氨基酚氧基锌络合物(I),其特征在于,R1~R2为氢,C1~C8直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基,卤素;R1~R2代表取代硅基SiR3R4R5时,R3~R5为C1~C6直链、支链或环状结构的烷基,C7~C12的单或多芳基取代烷基,C6~C12的芳基;
当A为式(II)时,R8为C1~C8直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基,C6~C12的芳基;
X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所述的含手性四氢吡咯骨架氨基酚氧基锌络合物(I),其特征在于,R1~R2为氢、甲基、异丙基、叔丁基、枯基、三苯甲基、三甲基硅基、三苯基硅基或卤素;R8为甲基、乙基、异丙基、正丁基、叔丁基、正己基、正辛基、环戊基、环己基、环辛基、苯基、苄基、苯乙基、二苯甲基、三苯甲基;X为二(三甲基硅)氨基。
5.根据权利要求4所述的方法,其特征在于,锌金属原料化合物为二{二(三甲基硅)氨基}锌;含手性四氢吡咯骨架氨基酚类配体化合物与锌金属原料化合物的摩尔比为1:1~1.5;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任一项所述的含手性四氢吡咯骨架氨基酚氧基锌络合物的应用,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,α-甲基三亚甲基环碳酸酯。
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任一项所述的含手性四氢吡咯骨架氨基酚氧基锌络合物为催化剂,使丙交酯聚合,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任一项所述的含手性四氢吡咯骨架氨基酚氧基锌络合物为催化剂,在醇存在的条件下,使丙交酯聚合,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,C7~C20的单或多芳基取代烷基醇。
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任一项所述的含手性四氢吡咯骨架氨基酚氧基锌络合物为催化剂,在加醇或不加醇的条件下,使ε-己内酯聚合;所述的醇为C1~C10直链、支链或环状结构的烷基醇,C7~C20的单或多芳基取代烷基醇。
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