CN103787943B - 手性胺基酚氧基锌、镁化合物及其制备方法和应用 - Google Patents
手性胺基酚氧基锌、镁化合物及其制备方法和应用 Download PDFInfo
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- CN103787943B CN103787943B CN201310184775.4A CN201310184775A CN103787943B CN 103787943 B CN103787943 B CN 103787943B CN 201310184775 A CN201310184775 A CN 201310184775A CN 103787943 B CN103787943 B CN 103787943B
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- Prior art keywords
- rac
- lactide
- zinc
- chiral amino
- compound
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- Expired - Fee Related
Links
- 239000011701 zinc Substances 0.000 title claims abstract description 153
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 64
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 150000002681 magnesium compounds Chemical class 0.000 title claims abstract description 28
- QCTXENUBAFDBER-UHFFFAOYSA-N [O].NC1=C(C=CC=C1)O Chemical compound [O].NC1=C(C=CC=C1)O QCTXENUBAFDBER-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000003446 ligand Substances 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- -1 amido phenol oxygen Chemical compound 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 9
- 150000002596 lactones Chemical group 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 350
- 238000006243 chemical reaction Methods 0.000 claims description 152
- 238000006116 polymerization reaction Methods 0.000 claims description 112
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 104
- 239000003054 catalyst Substances 0.000 claims description 76
- 239000011777 magnesium Chemical group 0.000 claims description 63
- 239000003208 petroleum Substances 0.000 claims description 50
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 229910052749 magnesium Inorganic materials 0.000 claims description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- JEYWNNAZDLFBFF-UHFFFAOYSA-N Nafoxidine Chemical compound C1CC2=CC(OC)=CC=C2C(C=2C=CC(OCCN3CCCC3)=CC=2)=C1C1=CC=CC=C1 JEYWNNAZDLFBFF-UHFFFAOYSA-N 0.000 claims description 19
- 229950002366 nafoxidine Drugs 0.000 claims description 19
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical group NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 15
- 125000003368 amide group Chemical group 0.000 claims description 15
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 229920002866 paraformaldehyde Polymers 0.000 claims description 14
- 239000012279 sodium borohydride Substances 0.000 claims description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 14
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical group C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960004217 benzyl alcohol Drugs 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- PHRABVHYUHIYGY-UHFFFAOYSA-N 1-methylnaphthalene Chemical group C1=CC=C2C([CH2])=CC=CC2=C1 PHRABVHYUHIYGY-UHFFFAOYSA-N 0.000 claims description 3
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 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
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 17
- 238000001953 recrystallisation Methods 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 11
- 239000004626 polylactic acid Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 3
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 180
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 150
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 130
- 239000002904 solvent Substances 0.000 description 67
- 229910052786 argon Inorganic materials 0.000 description 65
- 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 50
- 238000000710 polymer precipitation Methods 0.000 description 48
- 238000001291 vacuum drying Methods 0.000 description 48
- 238000009826 distribution Methods 0.000 description 47
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 42
- 230000015572 biosynthetic process Effects 0.000 description 32
- 238000003786 synthesis reaction Methods 0.000 description 32
- 239000007787 solid Substances 0.000 description 31
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- 229960000935 dehydrated alcohol Drugs 0.000 description 24
- 238000010992 reflux Methods 0.000 description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 18
- FZJCXIDLUFPGPP-UHFFFAOYSA-N propan-2-ol;toluene Chemical compound CC(C)O.CC1=CC=CC=C1 FZJCXIDLUFPGPP-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 14
- 239000000284 extract Substances 0.000 description 13
- 208000035126 Facies Diseases 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 12
- 235000002597 Solanum melongena Nutrition 0.000 description 12
- 244000061458 Solanum melongena Species 0.000 description 12
- 238000000605 extraction Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- BHIIWXJHALLFBD-UHFFFAOYSA-N oxolane;propan-2-ol Chemical compound CC(C)O.C1CCOC1 BHIIWXJHALLFBD-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- PAAISZSBTCBVJR-UHFFFAOYSA-N C(C1=CC=CC=C1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=C(C=CC(=C1)C)O Chemical compound C(C1=CC=CC=C1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=C(C=CC(=C1)C)O PAAISZSBTCBVJR-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical group NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- FMUYQRFTLHAARI-UHFFFAOYSA-N 2,4-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 FMUYQRFTLHAARI-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
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 0 CC*1(CCC2)[C@@]2C*(C2)*1Oc(c(N)c1)c2cc1N Chemical compound CC*1(CCC2)[C@@]2C*(C2)*1Oc(c(N)c1)c2cc1N 0.000 description 1
- PZFOMNSDIOFAPT-IBGZPJMESA-N CCN1[C@H](CN(Cc2ccccc2)Cc2cc(Cl)cc(Cl)c2O)CCC1 Chemical compound CCN1[C@H](CN(Cc2ccccc2)Cc2cc(Cl)cc(Cl)c2O)CCC1 PZFOMNSDIOFAPT-IBGZPJMESA-N 0.000 description 1
- ZNKKJQSIIWYNCD-UHFFFAOYSA-N CC[Zn]OC(C)C Chemical compound CC[Zn]OC(C)C ZNKKJQSIIWYNCD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000371997 Eriocheir sinensis Species 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000003275 alpha amino acid group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
- C07D207/09—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
-
- 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
- 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
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- 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
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一类多手性中心胺基酚氧基锌、镁化合物及其制备方法和在高活性、高选择性催化内酯开环聚合中的应用。其制备方法包括如下步骤:将中性配体直接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。本发明的手性胺基酚氧基锌、镁化合物是一种高效的内酯开环聚合催化剂,可用于催化丙交酯等的聚合反应;特别对于外消旋丙交酯可得到较高等规度或杂规度的聚乳酸。本发明的手性胺基酚氧基锌、镁化合物优点十分明显:原料易得,合成路线简单,产物收率高,具有较高的催化活性和立体选择性,能获得高规整度、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
本发明涉及一类手性胺基酚氧基锌、镁化合物,以及这类化合物在内酯聚合中的应用。
背景技术
作为一类可以代替传统高分子材料(聚烯烃)的聚合物,脂肪族聚酯因其良好的生物相容性和可降解性而受到了广泛关注。目前被大量研究的脂肪族聚酯包括聚乳酸、聚己内酯及聚丁内酯等。其中聚乳酸可以被自然界中微生物降解并参与自然界的碳循环,属于环境友好型聚合物。聚乳酸的生物相容性和优良的可加工性使其成为最具有发展前景的脂肪族聚酯,主要应用于工农业生产和生物医药领域(如药物的缓释材料、医用缝合材料等)。近年来,由催化剂引发乳酸二聚体(丙交酯)开环聚合得到的聚乳酸有着高效的可控度和较高的立体规整度而被大量研究。原料造价较低的丙交酯通过自身聚合或是与其他单体共聚可以得到多种结构性能的聚合物,这些聚合物的广阔应用前景吸引着各国科学家对这些内酯的聚合及相关催化剂的设计展开研究。
丙交酯的单体主要包括:L-丙交酯,D-丙交酯,内消旋丙交酯(meso-lactide)、1∶1的L-丙交酯和D-丙交酯混合物称为外消旋丙交酯(rac-lactide)。不同的单体通过金属络合物催化剂催化可以得到不同微观结构的聚乳酸。其中廉价易得的外消旋丙交酯通过开环聚合可以得到无规、杂规、嵌段等规聚合物和等规立体复合物。其中大多数催化剂催化外消旋丙交酯聚合主要得到无规聚丙交酯,为无定形体,机械强度和加工性能较差,使其工业应用受到大大限制。相对于其他规整度的聚乳酸,由外消旋丙交酯高等规选择性聚合得到的等规立体复合物有着较高的熔点和机械强度而得到广泛关注,研究开发外消旋丙交酯高活性、高等规选择性聚合催化剂成为该领域的研究热点。锌、镁的络合物对丙交酯聚合具有高催化活性、高可控性等特点,此外,锌、镁作为人体必需元素,其无色无毒以及具有生物相容性等特点也符合聚丙交酯在食品包装及医药领域的要求,锌、镁等环境友好型金属的络合物催化剂研究开发更成为该领域广泛关注的研究热点。
2001年Coates小组用β-二亚胺配体的锌、镁络合物(BDI)Zn(OiPr)和(BDI)Mg(OiPr)作为催化剂催化外消旋丙交酯聚合获得高分子量的杂规聚丙交酯和无规聚丙交酯(J.Am.Chem.Soc.2001,123,3229)。Hillmyer和Tolman研究组在2003年报道合成了单乙氧基双核锌络合物,该络合物对外消旋丙交酯开环聚合具有很高的催化剂活性,是至今为止锌络合物中活性最高的催化剂(J.Am.Chem.Soc.2003,125,11350)。Chisholm小组报道了多配位点醚键β-二亚胺配体锌、镁络合物,催化外消旋丙交酯聚合都得到了较高杂规度聚丙交酯(Inorg.Chem.2005,44,8004)。Lin小组合成了三齿席夫碱配体锌络合物,在THF溶剂中,能够催化外消旋丙交酯聚合得到杂规聚合物,降低温度至-55℃后杂规度可以达到0.91(Macromolecules,2006,39,3745)2007年,Carpentier小组合成了吡唑基胺基镁络合物并用来催化外消旋丙交酯开环聚合,显示出较好的催化活性,得到无规聚丙交酯(Polyhedron,2007,26,3817)。2010年,我们小组报道了多齿胺基酚氧基镁、锌络合物,其中镁络合物对丙交酯显示了超高活性,在甲苯中能够迅速催化大量丙交酯单体聚合,得到等规倾向的聚合物,Pm=0.60~0.65(Macromolecules,2010,43,6535-6537),锌络合物也得到等规倾向的聚合物(DaltonTrans.,2010,39,7897)。此外,为获得等规选择性,研究者尝试在络合物配体骨架上引入手性因素,如,Lin小组合成了含有手性环己二胺桥联的单阴离子Salen型配体镁络合物,催化外消旋丙交酯聚合得到略显等规的聚丙交酯,Pm=0.54~0.67(Polymer,2005,46,9784)。2009年,Mehrkhodavandi课题组合成了含有手性环己二胺结构的三齿席夫碱配体锌乙基络合物,其对外消旋丙交酯具有活性,但选择性很低(Organometallics,2009,28,1309)。2010年,Darensbourg报道了非环状单手性中心氨基酸衍生的酚亚胺类锌络合物,对外消旋丙交酯聚合表现出杂规选择性(Inorg.Chem.,2010,49,2360)。2012年,Otero报道了含有手性的杂异蟹型锌络合物,对外消旋丙交酯有活性聚合特征,得到杂规度不高的聚合物(Organometallics,2012,31,4191)。
金属络合物在外消旋丙交酯聚合领域中的应用已经取得了较大突破,通对对不同金属中心进行巧妙的配体设计,一定程度上实现了不同立体结构聚丙交酯的合成。作为环境友好型聚合物,人们在合成聚丙交酯时更倾向使用生物相容性金属的络合物(锌、镁等),但到目前为止,锌、镁等络合物作为内酯酯开环聚合催化剂,对外消旋丙交酯只表现出了较高的杂规选择性,具有较高等规选择性的催化剂还没有被报道。因此,有关锌、镁络合物催化剂的研究工作有待于进一步开展,以合成集高活性、高等规选择性为一体的高效催化剂。
发明内容
本发明目的之一在于公开一类手性胺基酚氧基锌、镁化合物。
本发明目的之二在于公开手性胺基酚氧基锌、镁化合物的制备方法。
本发明目的之三在于公开手性胺基酚氧基锌、镁化合物作为催化剂在内酯聚合中的应用。
本发明的技术构思:
目前,文献报道的高选择性锌、镁络合物对外消旋丙交酯开环聚合都是通过链端控制机理得到杂规聚乳酸。其中包括一些手性催化剂,它们没有利用手性中心控制机理表现出等规选择性的原因可能是配体的手性环境相对远离金属中心,在单体配位时并没有起到诱导选择性配位插入的作用。因此,本发明在配体结构中引入手性脯氨酸衍生的多手性中心骨架,该手性NNO三齿配体与金属配位后,能产生两个手性N原子和手性金属中心,加上配体本身的固有碳手性,可以得到多手性中心的金属络合物,以实现在单体与金属中心配位时起到手性诱导效果,从而获得高等规度选择性。此外,在多手性中心配体骨架基础上,改变其上各相关取代基,可以起到调整金属中心的空间位阻和路易斯酸性,从而筛选出集高活性、高选择性于一体的高效催化剂。
本发明提供的手性胺基酚类配体(I)及其金属锌、镁化合物(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,C1~C20直链或支链结构的烷氧基,C7~C30单或多芳基取代的烷基,C6~C18的芳基,卤素;R1~R2也可分别代表取代硅基SiR6R7R8,其中R6~R8分别为C1~C10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~C18的芳基,R6、R7和R8可以相同或不同;
R3~R4分别代表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;
R5代表C1~C10直链、支链或环状结构的烷基;R5代表胺基NR9R10,其中R9~R10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,R9和R10可以相同或不同;R5代表烷氧基OR11,其中R11为C1~C10直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基;
M代表锌、镁。
式(I)、(II)中,R1~R2优选为氢,C1~C8直链、支链或环状结构的烷基,C1~C8直链或支链结构的烷氧基,C7~C20单或多芳基取代的烷基,C6~C12的芳基,卤素;R1~R2代表取代硅基SiR6R7R8时,R6~R8优选为C1~C6直链、支链或环状结构的烷基,C7~C12单或多芳基取代的烷基,C6~C12的芳基;
R3~R4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;
R5代表C1~C6直链、支链或环状结构的烷基,二(三甲基硅)胺基,二(三乙基硅)胺基,二(二甲基氢硅)胺基;R5代表烷氧基OR11时,其中R11优选为C1~C6直链、支链或环状结构的烷基,苄基,(1-萘基)甲基,(9-蒽基)甲基。
式(I)、(II)中,更为特征的是,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;R3优选为甲基、乙基、异丙基、正丁基、正辛基、苄基;R4优选为甲基、异丙基、苄基、(1-萘基)甲基;R5优选为二(三甲基硅)胺基,乙基,正丁基,异丙氧基,苄氧基。
优选的手性胺基酚类配体,其结构式如下:
优选的手性胺基酚类配体的金属锌、镁化合物结构为:
本发明的手性胺基酚类配体(I)及其锌、镁化合物(II)制备方法如下步骤:
式中:
将式(III)所示的手性N-取代-2-氨基甲基四氢吡咯与取代醛O=CH-R4发生西佛碱反应生成亚胺,再加入还原剂还原成仲胺后,加入取代酚(IV)和多聚甲醛,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化合物(I)。
任选的,再将式(I)所示的手性胺基酚类配体化合物与锌或镁的金属原料化合物在有机介质中反应,生成手性胺基酚氧基锌或镁化合物,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化合物(II)。
上述制备方法中式(III)和(IV)中取代基R1~R4与满足本发明的手性胺基酚类配体(I)及其金属锌、镁化合物(II)的各相应基团的要求一致;金属原料化合物具有通式M(R5)(R12),M=Zn、Mg,R12为反应中离去的基团,其要求与R5一致,R5和R12可以相同或不同。
还原剂优选氢化铝锂或硼氢化钠。
锌或镁的金属原料化合物优选二乙基锌、二正丁基镁、乙基异丙氧基锌、二{二(三甲基硅)胺基}锌、二{二(三甲基硅)胺基}镁。
手性胺基酚类配体化合物与金属原料化合物的摩尔比为1∶0.5~1.5。
所说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。
本发明所说的手性胺基酚类配体的锌、镁化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。
以本发明手性胺基酚氧基锌、镁化合物为催化剂,使丙交酯在-39~130℃下聚合,聚合时催化剂与单体的摩尔比为1∶1~10000,优选1∶100~1000。
以本发明手性胺基酚氧基锌、镁化合物为催化剂,在醇存在的条件下,使丙交酯在-39~130℃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。
以本发明手性胺基酚氧基锌、镁化合物为催化剂,在醇存在下或不加醇,使β-丁内酯在-39~50℃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,同时具有较高的催化活性及高立体选择性,易获得高立体规整度、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
手性原料(S)-1-乙基-2-氨基甲基四氢吡咯,(S)-1-正丁基-2-氨基甲基四氢吡咯,(R)-1-正丁基-2-氨基甲基四氢吡咯,(S)-1-正辛基-2-氨基甲基四氢吡咯,(S)-1-苄基-2-氨基甲基四氢吡咯的合成可参考文献(Bioorg.Med.Chem.1998,6,1759)进行。
实施例1
配体L1的合成
在100mL茄型瓶中加入苯甲醛1.22g,30mL无水乙醇,(S)-1-乙基-2-氨基甲基四氢吡咯1.28g,加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2,4二氯苯酚1.63g,加热回流12小时。粗产品用硅胶进行柱层析分离得到红色液体L1(2.32g,59.0%)。
1HNMR(400MHz,CDCl3):δ7.22(m,6H),6.83(d,4J=2.4Hz),3.84(d,2J=14.0Hz,1H),3.65(d,2J=13.0Hz,1H),3.53(d,2J=14.0Hz,1H),3.39(d,2J=13.0Hz,1H),3.06(m,1H),2.80-2.70(m,1H),2.60-2.50(m,2H),2.60-2.50(m,1H),2.21-2.08(m,2H),2.01-1.94(m,1H),1.71-1.63(m,2H),1.45-1.38(m,1H),1.00(t,J=7.2Hz,3H);13C{1H}NMR(100MHz,CDCl3):δ152.4,136.0,129.8,128.7,127.9,127.1,124.8,121.6,62.4,59.1,58.1,57.7,53.5,49.0,30.0,22.4,13.6.Anal.Calcd.forC21H26Cl2N2O:C,64.12;H,6.66;N,7.12.Found:C,63.64;H,6.65;N,669%.
实施例2
配体L2的合成
在100mL茄型瓶中加入苯甲醛1.22g,30mL无水乙醇,(S)-1-乙基-2-氨基甲基四氢吡咯1.28g,加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2,4-二叔丁基苯酚2.06g,加热回流12小时。粗产品用硅胶进行柱层析分离得无色透明液体L2(1.95g,44.7%)。
1HNMR(400MHz,CDCl3):δ10.55(s,1H),7.35-7.23(m,5H),7.18(s,1H),6.85(s,1H),3.97(d,J=13.4Hz,1H),3.75(d,J=13.0Hz,1H),3.51(d,2J=13.4Hz,1H),3.37(d,2J=13.0Hz,1H),3.09-3.02(m,1H),2.71-2.63(m,1H),2.50-2.38(m,3H),2.11-2.01(m,1H),2.03-1.88(m,2H),1.67-1.55(m,2H),1.39(s,3H),1.37-1.28(m,1H),1.22(s,9H),1.03(t,J=7.1Hz,3H);13C{1H}NMR(100MHz,CDCl3):δ154.0,140.8,137.3,135.8,130.1,128.5,127.6,124.0,123.1,121.8,62.3,60.0,59.4,58.6,53.9,49.2,35.1,34.,31.9,30.4,29.8,22.6,14.0.Anal.Calcd.forC29H44N2O·(0.26CH3COOCH2CH3):C,78.51;H,10.11;N,6.10.Found:C,78.88;H,10.03;N,6.46%.
实施例3
配体L3的合成
在100mL茄型瓶中加入苯甲醛1.22g,30mL无水乙醇,(S)-1-乙基-2-氨基甲基四氢吡咯1.28g,加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,冷却至室温后,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2,4-二枯基苯酚3.30g,加热回流12小时。粗产品用硅胶进行柱层析分离得淡棕色液体L3(3.41g,60.9%)。
1HNMR(400MHz,CDCl3):δ7.16(d,J=12.6Hz,17H),6.66(d,J=1.8Hz,1H),3.80(d,2J=13.6Hz,1H),3.46(d,2J=13.8Hz,1H),3.33(d,2J=13.6Hz,1H),3.13(d,2J=12.8Hz),2.97-2.86(m,1H),2.55(dq,J=14.7,7.3Hz,1H),2.28(dt,J=15.7,7.9Hz,3H),2.01-1.92(m,2H),1.60(t,J=16.1Hz,12H),1.31-1.50(m,2H),0.90(t,J=7.2Hz,3H);13CNMR(100MHz,CDCl3):δ153.5,151.4,139.9,136.9,135.2,130.0,128.5,128.2,127.9,127.6,127.3,126.8,125.9,125.4,124.8,121.8,62.0,59.6,58.9,57.91,53.6,48.9,42.4,42.0,3.1,30.3,30.0,28.6,22.4,13.7.Anal.Calcd.forC42H56N2O2:C,83.52;H,8.63;N,5.00.Found:C,83.32;H,8.56;N,4.65%.
实施例4
配体L4的合成
在100mL茄型瓶中加入苯甲醛1.22g,30mL无水乙醇,(S)-1-乙基-2-氨基甲基四氢吡咯1.28g,加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,冷却至室温后,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2-三苯甲基-4-二叔丁基苯酚3.50g,加热回流12小时。粗产品用硅胶进行柱层析分离得白色固体L4(3.96g,68.2%)。
1HNMR(400MHz,CDCl3):δ10.3(s,1H),7.28-7.20(m,15H),7.18-7.14(m,3H),6.95(s,1H),6.93-6.87(m,2H),6.82(s,1H),3.89(d,2J=13.5Hz,1H),3.54(d,2J=12.8Hz,1H),3.50(d,2J=13.5Hz,1H),3.29(d,2J=12.8Hz,1H),3.03-2.92(m,1H),2.70-2.59(m,1H),2.30-2.21(m,3H),2.20(s,1H),2.08-2.00(m,1H),1.94(dd,1H,2J=17.3,3J=9.0Hz),1.62-1.50(m,1H),1.48-1.38(m,2H),1.06-0.99(m,1H),0.95(t,3J=7.2Hz,3H);13C{1H}NMR(100MHz,CDCl3):154.1,146.3,137.3,133.8,131.5,131.0,130.3,129.2,128.4,127.4,127.1,126.6,125.5,122.8,63.5,62.5,59.8,59.1,57.2,53.7,49.1,29.9,22.6,21.1,13.9.Anal.Calcd.forC41H44N2O:C,84.79;H,7.64;N,4.82.Found:C,84.37;H,7.61;N,4.77%.
实施例5
配体L5的合成
在100mL茄型瓶中加入苯甲醛1.22g,30mL无水乙醇,(S)-1-正丁基-2-氨基甲基四氢吡咯1.56g,加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,冷却至室温后,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2,4-二氯苯酚1.63g,加热回流12小时。粗产品用硅胶进行柱层析分离得红色液体L5(2.18g,51.7%)。
1HNMR(400MHz,CDCl3):δ7.38-7.22(m,6H),6.90(d,J=2.4Hz,1H),3.90(d,J=14.1Hz,1H),3.72(d,J=13.0Hz,1H),3.61(d,J=14.1Hz,1H),3.47(d,J=13.0Hz,1H),3.16-3.05(m,1H),2.67-2.44(m,4H),2.15-2.03(m,2H),1.98(td,J=15.8,7.9Hz,1H),1.66(dt,J=16.7,8.3Hz,2H),1.51-1.35(m,3H),1.34-1.19(m,2H),0.88(t,J=7.3Hz,3H).13C{1H}NMR(100MHz,CDCl3):δ152.62,136.18,130.00,128.84,128.07,127.28,124.95,123.51,121.77,62.88,59.31,58.27,57.93,55.36,54.24,30.99,30.16,22.69,20.94,14.20.Anal.Calcd.forC23H30Cl2N2O:C,65.55;H,7.18;N,6.65.Found:C,65.53;H,7.07;N,6.52%.
实施例6
配体L6的合成
在100mL茄型瓶中加入苯甲醛1.22g,30mL无水乙醇,(S)-1-正丁基-2-氨基甲基四氢吡咯1.56g,加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,冷却至室温后,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2.06g2,4-二叔丁基苯酚,加热回流12小时。粗产品用硅胶进行柱层析分离得无色透明液体L6(2.86g,61.5%)。
1HNMR(400MHz,CDCl3):δ10.63(s,1H),7.38-7.15(m,7H),6.85(d,J=2.3Hz,1H),3.55(d,J=13.5Hz,1H),3.40(d,J=13.0Hz,1H),3.13-2.99(m,1H),2.68-2.56(m,1H),2.56-2.41(m,3H),2.11-1.92(m,3H),1.63(tt,J=9.6,5.9Hz,2H),1.48-1.32(m,3H),1.44(s,9H),1.27(s,9H),1.31-1.20(m,2H),0.88(t,J=7.3Hz,3H).13C{1H}NMR(100MHz,CDCl3):δ154.03,140.74,137.37,135.76,130.07,128.55,127.62,123.95,123.08,121.81,62.65,59.99,59.39,58.60,55.48,54.47,35.08,34.31,31.89,31.20,30.42,29.78,22.75,21.01,14.24.Anal.Calcd.forC31H48N2O:C,80.12;H,10.43;N,6.03.Found:C,80.31;H,10.21;N,6.00%.
实施例7
配体L7的合成
在100mL茄型瓶中加入苯甲醛1.22g,30mL无水乙醇,(S)-1-正丁基-2-氨基甲基四氢吡咯1.56g,加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,冷却至室温后,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2-三苯甲基-4-甲基苯酚3.50g,加热回流12小时。粗产品用甲醇重结晶得白色固体配体L7(5.46g,89.8%)。
1HNMR(400MHz,C6D6):δ10.59(s,1H),7.56(d,J=7.5Hz,6H),7.35(d,4J=1.6Hz,1H),7.14-7.08(m,9H),7.02(t,3J=7.3Hz,3H),6.93-6.88(d,3J=6.4Hz,2H),6.74(d,4J=1.6Hz,1H),3.62(d,2J=13.4Hz,1H),3.42(d,2J=13.4Hz,1H),3.29(d,2J=12.8Hz,1H),3.15(d,2J=12.8Hz,1H),2.82-2.75(m,1H),2.49-2.39(m,1H),2.24(d,3J=5.3Hz,2H),2.15(s,3H),2.11-2.03(m,1H),1.83-1.75(m,1H),1.68(dd,2J=16.6,3J=9.0Hz,1H),1.38(m,1H),1.33-1.11(m,6H),1.05(m,1H),0.84(t,3J=7.0Hz).13C{1H}NMR(100MHz,C6D6):154.9,147.2,138.4,134.8,132.3,131.7,130.1129.9,128.9,127.8,127.7,127.1,126.1,123.1,64.3,63.3,60.4),59.6,57.4,55.5,54.3,31.6,30.1,23.1,21.4,21.3,14.7.Anal.Calcd.forC43H48N2O:C,84.82;H,7.95;N,4.60.Found:C,84.75;H,7.80;N,4.62%.
实施例8
配体L8的合成
在100mL茄型瓶中加入1-萘甲醛1.72g,30mL无水乙醇,(S)-1-正丁基-2-氨基甲基四氢吡咯1.56g,加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,冷却至室温后,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2-三苯甲基-4-甲基苯酚3.50g,加热回流12小时。粗产品经柱层析分离得白色固体L8(3.12g,47.4%)。
1HNMR(400MHz,CDCl3):δ10.30(s,1H),7.83(dd,J=16.4,8.0Hz,2H),7.73(d,J=8.2Hz,1H),7.46-7.35(m,2H),7.34-7.29(m,1H),7.24(dd,J=6.7,5.2Hz,5H),7.19-7.07(m,11H),6.95(d,J=1.6Hz,1H),6.87(d,J=1.6Hz,1H),4.06(d,J=13.0Hz,1H),3.78(d,J=13.1Hz,1H),3.64(dd,J=29.2,13.4Hz,2H),2.78(t,J=7.0Hz,1H),2.55-2.36(m,3H),2.18(s,3H),2.12(d,J=3.9Hz,1H),1.84-1.72(m,2H),1.33-1.17(m,4H),1.10(tt,J=9.5,5.8Hz,4H),0.99-0.87(m,1H),0.78(t,J=7.0Hz,3H).
实施例9
配体L9的合成
在100mL茄型瓶中加入丙酮0.64g,30mL无水乙醇,(S)-1-正丁基-2-氨基甲基四氢吡咯1.56g(10mmol),加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,冷却至室温后,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2-三苯甲基-4-甲基苯酚3.50g,加热回流12小时。粗产品经柱层析分离得白色固体L9(2.08g,37.1%)。
1HNMR(400MHz,CDCl3):δ7.26-7.16(m,12H),7.14-7.08(m,3H),6.88(d,J=1.8Hz,1H),6.73(d,J=1.7Hz,1H),3.78(d,J=14.0Hz,1H),3.55(d,J=14.0Hz,1H),3.01(dd,J=11.8,5.7Hz,1H),2.82-2.69(m,1H),2.65-2.54(m,1H),2.35(q,J=7.5Hz,1H),2.27-2.18(m,2H),2.15(s,3H),2.01(ddd,J=22.9,11.3,7.0Hz,2H),1.59-1.47(m,3H),1.44-1.31(m,2H),1.31-1.12(m,4H),0.87(t,J=7.2Hz,3H),0.84(d,J=6.7Hz,6H).13C{1H}NMR(100MHz,CDCl3):δ154.58,146.32,133.62,131.39,130.58,128.65,127.03,126.34,125.30,122.84,63.38,63.04,55.51,54.50,53.07,49.54,31.21,29.79,22.78,21.07,14.27.Anal.Calcd.forC39H48N2O:C,83.52;H,8.63;N,4.60.Found:C,83.30;H,8.73;N,4.85%.
实施例10
配体L10的合成
在100mL茄型瓶中加入苯甲醛1.22g,30mL无水乙醇,(S)-1-正辛基-2-氨基甲基四氢吡咯2.12g,加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,冷却至室温后,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2,4-二氯苯酚1.63g,加热回流12小时。粗产品用硅胶进行柱层析分离得到红色液体L10(2.41g,50.5%)。
1HNMR(400MHz,CDCl3):δ7.37-7.23(m,6H),6.90(d,J=2.4Hz,1H),3.90(d,J=14.1Hz,1H),3.72(d,J=13.0Hz,1H),3.61(d,J=14.1Hz,1H),3.47(d,J=13.0Hz,1H),3.14-3.05(m,1H),2.67-2.43(m,4H),2.14-2.03(m,2H),1.98(td,J=15.7,7.9Hz,1H),1.66(dt,J=16.4,8.1Hz,2H),1.51-1.34(m,3H),1.34-1.16(m,11H),0.88(t,J=6.8Hz,3H).Anal.Calcd.forC27H38Cl2N2O:C,67.91;H,8.02;N,5.87.Found:C,68.02;H,8.02;N,5.51%.
实施例11
配体L11的合成
在100mL茄型瓶中加入苯甲醛1.22g,30mL无水乙醇,(S)-1-正辛基-2-氨基甲基四氢吡咯2.12g,加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,冷却至室温后,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2-三苯甲基-4-甲基苯酚3.50g,加热回流12小时。粗产品经重结晶得白色固体L11(4.30g,66.5%)
1HNMR(400MHz,CDCl3):δ10.27(s,1H),7.36(d,J=4.4Hz,1H),7.27-7.09(m,17H),6.91(d,J=1.7Hz,1H),6.87(dd,J=6.5,2.8Hz,2H),6.79(d,J=1.7Hz,1H),3.83(d,J=13.5Hz,1H),3.54(d,J=13.6Hz,1H),3.45(d,J=12.8Hz,1H),3.27(d,J=12.8Hz,1H),2.99-2.84(m,1H),2.46(td,J=11.1,5.8Hz,1H),2.37(d,J=10.1Hz,1H),2.32-2.21(m,2H),2.17(s,3H),1.96-1.85(m,2H),1.60-1.49(m,1H),1.43(ddd,J=16.8,7.4,2.4Hz,2H),1.35-1.10(m,13H),0.99(ddd,J=17.1,10.4,5.4Hz,1H),0.88(t,J=7.0Hz,3H).13CNMR(100MHz,CDCl3):δ154.09,146.34,137.30,133.77,131.43,130.97,130.23,129.16,128.37,127.37,127.11,126.57,125.44,122.77,63.46,62.73,59.83,59.06,57.13,55.64,54.23,32.05,29.86,29.68,29.49,28.85,27.85,22.89,22.61,21.11,14.34.Anal.Calcd.forC47H56N2O:C,84.89;H,8.49;N,4.21.Found:C,84.95;H,8.57;N,4.27%.
实施例12
配体L12的合成
在100mL茄型瓶中加入苯甲醛1.22g,30mL无水乙醇,(R)-1-乙基-2-氨基甲基四氢吡咯1.56g,加热回流24小时。加入0.76g硼氢化钠,搅拌3小时,冷却至室温后,倒入水中、二氯甲烷萃取有机相,无水硫酸镁干燥,抽除溶剂得淡黄色粘稠液体。加入无水乙醇30mL,多聚甲醛0.6g,2-三苯甲基-4-甲基苯酚3.50g,加热回流12小时。粗产品用甲醇重结晶得白色固体配体L12(5.21g,85.6%)。
1HNMR(400MHz,CDCl3):δ1HNMR(400MHz,CDCl3)δ10.28(s,1H),7.26-7.10(m,J=13.6,7.1Hz,18H),6.91(s,1H),6.89-6.82(m,2H),6.79(s,1H),3.82(d,4J=13.5Hz,1H),3.55(d,4J=13.5Hz,1H),3.44(d,4J=12.8Hz,1H),3.28(d,4J=12.7Hz,1H),2.95-2.85(m,1H),2.49(td,4J=10.8,3J=5.4Hz,1H),2.41-2.20(m,3H),2.17(s,3H),1.90(dd,4J=16.8,3J=9.3Hz,2H),1.57-1.47(m,1H),1.47-1.35(m,2H),1.34-1.10(m,4H),1.14-0.93(m,1H),0.83(t,J=7.0Hz,3H).13C{1H}NMR(100MHz,CDCl3):154.9,147.2,138.4,134.8,132.3,131.7,130.1129.9,128.9,127.8,127.7,127.1,126.1,123.1,64.3,63.3,60.4),59.6,57.4,55.5,54.3,31.6,30.1,23.1,21.4,21.3,14.7.Anal.Calcd.forC43H48N2O:C,84.82;H,7.95;N,4.60.Found:C,84.83;H,7.80;N,4.54%.
实施例13
锌络合物Zn1的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L1(0.590g,1.50mmol)的甲苯溶液,室温搅拌,析出白色固体。过滤,抽去溶剂得白色固体Zn1(0.473g,产率:51.0%),有两种异构体,比例为2∶3。
NMRspectroscopicdataforisomer1a:1HNMR(400MHz,C6D6):δ7.45(d,4J=2.7Hz,1H),7.13-7.11(m,3H),7.01(dd,3J=6.5,4J=3.0Hz,2H),6.44(d,4J=2.7Hz,1H),4.07(d,2J=13.8Hz,1H),3.75(d,2J=12.7Hz,1H),3.64(d,2J=13.8Hz,1H),2.76(d,2J=12.7Hz,1H),2.62-2.52(m,1H),2.51-2.44(m,1H),2.41-2.30(m,2H),2.02(m,1H),1.78-1.60(m,2H),1.16(t,3J=7.1Hz,3H),1.02-0.92(m,2H),0.88-0.78(m,1H),0.53(s,18H).0.38-0.32(m,1H),13C{1H}NMR(100MHz,C6D6):162.5,132.7,132.4,131.7,130.8,129.2,125.8,125.0,117.1,66.7,64.9,59.5,59.1,50.5,50.4,25.6,20.8,14.5,7.5.NMRspectroscopicdataforisomer1b:1HNMR(400MHz,C6D6):δ7.12(d,4J=2.7Hz,1H),7.13-7.11(m,3H),6.81(dd,3J=7.2,4J=2.1Hz,2H),6.37(d,4J=2.7Hz,1H),4.07(d,2J=13.3Hz,2H),3.85(d,2J=14.0Hz,1H),2.89(d,2J=12.9Hz,1H),2.89-2.76(m,1H),2.62-2.44(m,1H),2.30-2.24(m,2H),1.93-1.84(m,1H),1.78-1.60(m,2H),1.14(t,J=7.2Hz,3H),1.02-0.92(m,1H),0.71-0.65(m,1H),0.54(s,18H),0.44-0.38(m,1H),0.38-0.33(m,1H),13C{1H}NMR(100MHz,C6D6):δ130.9,130.7,129.9,129.4,129.3,129.1,128.5,126.3,122.6,116.9,64.9,63.4,59.0,58.6,49.8,48.9,25.0,19.9,13.7,7.3.Anal.Calcd.forC27H43Cl2N3OSi2Zn:C,52.46;H,7.01;N,6.80.Found:C,52.47;H,7.07;N,6.86%.
实施例14
锌络合物Zn2的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L2(0.655g,1.50mmol)的甲苯溶液,室温搅拌,用正己烷重结晶,得白色固体Zn2(0.585g,产率:59.0%),有两种异构体,比例为1∶1。
1HNMR(400MHz,C6D6):δ7.65-7.60(m,1H),7.59-7.55(m,1H),7.30-7.20(m,2H),7.17-7.12(m,3H),7.10-7.04(m,3H),6.97(d,4J=2.3Hz,1H),6.92-6.86(m,2H),6.66(d,4J=2.3Hz,1H),4.33(d,2J=12.4Hz,1H),4.31(d,J=13.9Hz,1H),4.25(d,2J=14.0Hz,1H),4.08(d,J=14.0Hz,1H),3.95(d,2J=13.9Hz,1H),3.64(d,J=12.3Hz,1H),3.29(d,2J=12.3Hz,2H),3.13(d,J=12.4Hz,1H),3.11-3.02(m,1H),2.86-2.74(m,1H),2.52-2.44(m,3H),2.39(m,2H),2.32(m,2H),2.23(m,1H),2.02(dd,J=14.3,4.1Hz,1H),1.96-1.91(m,1H),1.87(s,9H),1.81(s,9H),1.76-1.73(m,1H),1.61-1.55(m,2H),1.53-1.50(m,1H),1.46(s,9H),1.39-1.33(m,2H),1.27(s,9H),1.23-1.20(m,1H),1.20(t,3J=7.0Hz,3H),1.16-1.12(m,1H),0.94(t,3J=7.1Hz,3H),0.71-0.65(m,1H),0.59(s,18H),0.48(s,18H).13C{1H}NMR(100MHz,C6D6):δ165.1,164.7,138.9,138.5,138.5,135.1,134.9,132.6,132.4,131.7,129.2,129.1,129.1,128.9,127.1,126.8,125.3,124.9,120.7,120.2,64.2,61.7,60.7,59.7,59.1,57.9,54.0,51.2,49.6,49.4,36.3,36.3,34.5,34.3,32.7,32.5,30.9,30.6,26.6,24.9,21.8,19.6,14.1,13.2,7.7,7.4.Anal.Calcd.forC35H61N3OSi2Zn:C,63.55;H,9.30;N,6.35.Found:C,63.84;H,9.07;N,5.87%.
实施例15
锌络合物Zn3的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L3(0.840g,1.50mmol)的甲苯溶液,室温搅拌,用正己烷重结晶,得白色固体Zn3(0.477g,产率:40.5%),有两种异构体,比例为1∶1.2。
Anal.Calcd.forC45H63N3OSi2Zn:C,68.80;H,8.34;N,5.35.Found:C,68.60;H,8.08;N,5.09%.
实施例16
锌络合物Zn4的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L4(0.871g,1.50mmol)的甲苯溶液,室温搅拌,用甲苯和正己烷混合溶剂重结晶,得白色固体Zn4(0.631g,产率:52.3%),有两种异构体,比例为7∶1。
1HNMR(400MHz,C6D6):δ7.67-7.55(m,6H),7.39(d,4J=2.2Hz,1H),7.14-7.09(m,7H),7.07-6.87(m,7H),6.40(d,4J=2.2Hz,1H),4.38(d,2J=12.3Hz,1H),4.21(d,2J=14.2Hz,1H),4.07(d,2J=14.2Hz,1H),3.27(d,2J=12.3,1H),3.02-2.93(m,1H),2.26-2.15(m,1H),2.05(s,3H),1.98-1.89(m,2H),1.86-1.75(m,1H),1.39-1.29(m,1H),1.18-1.05(m,2H),1.02(t,3J=7.1Hz,3H),0.97-0.83(m,1H),0.60-0.52(m,1H),0.50-0.40(m,1H),0.35(s,18H).13C{1H}NMR(100MHz,C6D6):δ165.0,135.8,134.9,132.8,132.7,132.4,131.6,129.7,129.2,128.9,127.8,127.5,126.0,125.4,120.8,120.7,64.7,62.9,59.7,58.3,49.8,48.7,48.4,24.9,21.1,20.0,14.2,7.6.Anal.Calcd.forC47H61N3OSi2Zn:C,70.07;H,7.63;N,5.22.Found:C,69.95;H,7.46;N,4.56%.
实施例17
锌络合物Zn5的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L5(0.632g,1.50mmol)的甲苯溶液,室温搅拌,析出白色固体,过滤,抽去溶剂得白色固体Zn5(0.480g,产率:49.5%),两种异构体,比例为3∶1。
1HNMR(400MHz,C6D6):δ7.45(d,J=2.7Hz,1H),7.13-7.10(m,3H),7.01(dd,J=6.4,2.8Hz,2H),6.42(d,J=2.7Hz,1H),4.10(s,1H),3.83(d,J=12.7Hz,1H),3.61(d,J=13.8Hz,1H),2.72(d,J=12.7Hz,1H),2.53(dd,J=10.7,6.7Hz,2H),2.48-2.34(m,2H),2.21-2.10(m,1H),1.99(t,J=13.2Hz,1H),1.75(dd,J=13.6,7.1Hz,1H),1.64(ddd,J=17.0,7.6,4.9Hz,2H),1.30(ddd,J=17.4,12.1,6.0Hz,1H),1.19(dd,J=11.7,6.0Hz,2H),1.03(d,J=7.2Hz,3H),0.83(ddd,J=17.7,10.5,6.7Hz,1H),0.53(s,18H).Anal.Calcd.forC29H47Cl2N3OSi2Zn:C,53.90;H,7.33;N,6.50.Found:C,53.84;H,7.24;N,6.44%.
实施例18
锌络合物Zn6的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L6(0.697g,1.50mmol)的甲苯溶液,室温搅拌,用正己烷重结晶,得白色固体Zn6(0.516g,产率:49.9%),两种异构体,比例为3∶2。
1HNMR(400MHz,C6D6):δ7.57(d,J=2.5Hz,1H),7.05(dt,J=5.3,4.2Hz,3H),6.89-6.82(m,2H),6.68(d,J=2.5Hz,1H),4.36(d,J=12.2Hz,1H),4.26(d,J=14.1Hz,1H),4.17(d,J=14.1Hz,1H),3.36(d,J=12.3Hz,1H),3.16-3.08(m,1H),2.60-2.49(m,2H),2.40(td,J=12.7,6.1Hz,2H),2.23(dd,J=16.4,10.3Hz,2H),2.09(dd,J=14.4,4.2Hz,1H),1.97(dd,J=11.9,4.3Hz,1H),1.82(s,9H),1.61-1.51(m,1H),1.27(s,9H),1.26-1.14(m,3H),1.13-1.02(m,3H),0.98(t,J=7.2Hz,3H),0.60(s,18H).Anal.Calcd.ForC37H65N3OSi2Zn:C,64.45;H,9.50;N,6.09.Found:C,64.41;H,9.39;N,6.00%.
实施例19
锌络合物Zn7的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L7(0.912g,1.50mmol)的甲苯溶液,室温搅拌,用甲苯和正己烷重结晶,得白色固体Zn7(0.749g,产率:60%)。
1HNMR(400MHz,C6D6):δ7.62(m,6H),7.40(d,4J=2.2Hz,1H),7.14-7.07(m,9H),7.02-6.89(m,5H),6.46-6.35(d,4J=2.2Hz,1H),4.38(d,2J=12.3Hz,1H),4.25(d,2J=14.2Hz,1H),4.12(d,2J=14.2Hz,1H),3.27(d,2J=12.3Hz,1H),3.06-2.98(m,1H),2.28-2.18(m,1H),2.05(s,3H),1.98-1.91(m,2H),1.86-1.76(m,2H),1.49-1.31(m,2H),1.23-1.06(m,3H),1.02-0.95(m,1H),0.98(t,3J=7.1Hz,3H),0.88-0.79(m,1H),0.67-0.54(m,1H),0.52-0.43(m,1H),0.35(s,18H.13C{1H}NMR(100MHz,C6D6):δ165.2,135.6,134.9,132.9,132.7,131.7,129.2,128.3,127.9,125.4,120.9,120.7,64.8,63.6,59.7,58.4,56.3,49.1,48.5,30.9,25.1,21.2,21.1,19.9,14.6,7.6.Anal.Calcd.forC49H64N2OSi2Zn:C,70.60;H,7.86;N,5.04;Found:C,71.24;H,8.10;N,4.69%.
实施例20
锌络合物Zn8的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L8(0.912g,1.50mmol)的甲苯溶液,室温搅拌,用甲苯和正己烷重结晶,得白色固体Zn8(0.624g,产率:47.1%)。
1HNMR(400MHz,C6D6):δ8.34(d,J=8.6Hz,1H),7.70-7.46(m,9H),7.41(d,J=8.9Hz,2H),7.24(t,J=7.6Hz,2H),7.11-6.86(m,9H),6.11(s,1H),4.97(d,J=14.6Hz,1H),4.57(t,J=14.6Hz,2H),3.17(d,J=11.9Hz,2H),2.28(ddd,J=28.7,17.9,17.3Hz,3H),2.03-1.88(m,6H),1.74(dd,J=12.0,8.5Hz,1H),1.41-1.07(m,7H),1.02(t,J=6.7Hz,3H),0.96-0.77(m,4H),0.51(t,J=18.3Hz,2H),0.41(s,18H).Anal.Calcd.forC53H67N2OSi2Zn·0.5C7H8:C,72.99;H,7.70;N,4.52;Found:C,72.83;H,7.53;N,4.36%.
实施例21
锌络合物Zn9的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L9(0.840g,1.50mmol)的甲苯溶液,室温搅拌,析出白色固体,过滤,抽去溶剂得白色固体Zn9(0.813g,产率:69.0%),两种异构体,比例8∶1。
1HNMR(400MHz,C6D6):δ7.70-7.48(m,5H),7.58-7.40(m,1H),7.12(m,J=7.4Hz,5H),7.03(dd,J=17.2,7.3Hz,2H),6.95(t,J=7.2Hz,3H),6.66(d,J=2.0Hz,1H),4.16(d,J=11.8Hz,1H),3.13(dt,J=12.8,6.3Hz,1H),2.92(d,J=11.8Hz,1H),2.61-2.49(m,1H),2.10(s,3H),2.07-1.95(m,1H),1.66-1.57(m,2H),1.54(d,J=6.6Hz,3H),1.29-1.15(m,3H),1.05(d,J=6.4Hz,1H),1.00(d,J=4.0Hz,3H),0.70(dd,J=16.3,10.0Hz,1H),0.64(d,J=6.2Hz,3H),0.54(d,J=7.2Hz,1H),0.31(s,18H).Anal.Calcd.forC45H65N2OSi2Zn·1C7H8:C,71.16;H,8.38;N,4.79;Found:C,70.96;H,8.40;N,4.70%.
实施例22
锌络合物Zn10的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L10(0.715g,1.50mmol)的甲苯溶液,室温搅拌,放入冰箱后析出淡黄色固体,用正己烷洗涤固体,抽去溶剂得白色固体Zn10(0.578g,产率:54.9%),两种异构体,比例为4∶1。
1HNMR(400MHz,C6D6):δ7.45(d,J=2.6Hz,1H),7.12(d,J=3.6Hz,3H),7.01(dd,J=6.1,2.7Hz,2H),6.42(d,J=2.6Hz,1H),4.09(d,J=13.9Hz,1H),3.85(d,J=12.6Hz,1H),3.64(d,J=13.9Hz,1H),2.74(d,J=12.6Hz,1H),2.59(dt,J=15.2,9.3Hz,2H),2.45(ddd,J=26.0,12.8,5.1Hz,2H),2.20(dd,J=13.6,8.5Hz,1H),2.02(t,J=13.2Hz,1H),1.85-1.75(m,1H),1.68(dd,J=13.6,4.5Hz,1H),1.48-1.28(m,11H),1.27-1.17(m,2H),1.10-1.00(m,2H),0.95(t,J=6.7Hz,3H),0.90-0.81(m,2H),0.54(s,18H).Anal.Calcd.forC33H55Cl2N3OSi2Zn:C,56.44;H,7.89;N,5.89.Found:C,56.32;H,7.69;N,5.57%.
实施例23
锌络合物Zn11的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L11(0.997g,1.50mmol)的甲苯溶液,室温搅拌,用甲苯和正己烷重结晶,得白色固体Zn11(0.856g,产率:66.6%)。
1HNMR(400MHz,C6D6):δ7.87-7.50(m,6H),7.41(d,J=2.2Hz,1H),7.15-7.07(m,9H),7.02-6.88(m,6H),6.39(d,J=2.2Hz,1H),4.38(d,J=12.2Hz,1H),4.25(d,J=14.2Hz,1H),4.14(d,J=14.2Hz,1H),3.27(d,J=12.3Hz,1H),3.05(dt,J=12.8,6.5Hz,1H),2.29(dd,J=13.3,7.2Hz,1H),2.06(s,3H),2.00-1.93(m,2H),1.86(q,J=14.9Hz,2H),1.53-1.27(m,12H),1.27-1.12(m,4H),0.94(t,J=6.9Hz,3H),0.88-0.79(m,3H),0.60(dd,J=18.1,8.2Hz,1H),0.51(d,J=5.1Hz,1H),0.36(s,18H).Anal.Calcd.forC53H73N2OSi2Zn·0.5C7H8:C,72.51;H,8.29;N,4.49;Found:C,72.19;H,8.03;N,4.01%.
实施例24
锌络合物Zn12的合成
在氩气保护下,于50mLSchlenk瓶内加入Zn[N(SiMe3)2]2(0.579g,1.50mmol),3mL甲苯,再慢慢加入配体L12(0.912g,1.50mmol)的甲苯溶液,室温搅拌,用甲苯和正己烷重结晶,得白色固体Zn12(0.862g,产率:68.9%)。
1HNMR(400MHz,C6D6):δ7.62(m,6H),7.40(d,4J=2.2Hz,1H),7.14-7.07(m,9H),7.02-6.89(m,5H),6.46-6.35(d,4J=2.2Hz,1H),4.38(d,2J=12.3Hz,1H),4.25(d,2J=14.2Hz,1H),4.12(d,2J=14.2Hz,1H),3.27(d,2J=12.3Hz,1H),3.06-2.98(m,1H),2.28-2.18(m,1H),2.05(s,3H),1.98-1.91(m,2H),1.86-1.76(m,2H),1.49-1.31(m,2H),1.23-1.06(m,3H),1.02-0.95(m,1H),0.98(t,3J=7.1Hz,3H),0.88-0.79(m,1H),0.67-0.54(m,1H),0.52-0.43(m,1H),0.35(s,18H);13C{1H}NMR(100MHz,C6D6):δ165.2,135.6,134.9,132.9,132.7,131.7,129.2,128.3,127.9,125.4,120.9,120.7,64.8,63.6,59.7,58.4,56.3,49.1,48.5,30.9,25.1,21.2,21.1,19.9,14.6,7.6.Anal.Calcd.forC49H64N2OSi2Zn·C7H8:C,72.65;H,7.95;N,4.54;Found:C,72.65;H,7.83;N,4.49%.
实施例25
镁络合物Mg1的合成
在氩气保护下,于50mLSchlenk瓶内加入Mg[N(SiMe3)2]2(0.520g,1.50mmol),3mL甲苯,再慢慢加入配体L1(0.590g,1.50mmol)的甲苯溶液,室温搅拌,析出白色固体,过滤,抽去溶剂得白色固体Mg1(0.409g,产率:47.3%),两种异构体,比例为2.5∶1。
1HNMR(400MHz,C6D6):δ7.46(d,J=2.2Hz,1H),7.15-7.06(m,4H),6.85-6.79(m,1H),6.61(d,J=2.6Hz,1H),3.84(d,J=13.5Hz,1H),3.45(d,J=13.6Hz,1H),3.37(d,J=13.0Hz,1H),2.80(d,J=13.0Hz,1H),2.66(dt,J=13.4,6.4Hz,1H),2.47-2.35(m,2H),2.21(dq,J=14.5,7.2Hz,1H),1.99(dt,J=12.8,10.3Hz,2H),1.78(dd,J=12.9,5.6Hz,1H),1.57-1.52(m,1H),1.00(d,J=7.2Hz,3H),0.91(dd,J=14.8,6.5Hz,1H),0.52(s,18H).Anal.Calcd.forC27H43Cl2MgN3OSi2:C,56.20;H,7.51;N,7.28.Found:C,55.58;H,7.40;N,7.23%.
实施例26
镁络合物Mg3的合成
在氩气保护下,于50mLSchlenk瓶内加入Mg[N(SiMe3)2]2(0.520g,1.50mmol),3mL甲苯,再慢慢加入配体L3(0.840g,1.50mmol)的甲苯溶液,室温搅拌,用正己烷重结晶,得白色固体Mg3(0.398g,产率:35.6%),两种异构体,比例为10∶1。
1HNMR(400MHz,C6D6):δ7.72(s,1H),7.56(d,J=7.6Hz,2H),7.47(d,J=7.6Hz,2H),7.22(dd,J=32.8,7.6Hz,5H),7.18-7.02(m,6H),6.84(s,1H),4.18(d,J=13.7Hz,1H),3.90(d,J=13.8Hz,1H),3.65(d,J=12.7Hz,1H),3.49-3.36(m,1H),2.75-2.60(m,1H),2.51(d,J=12.9Hz,1H),2.38-2.25(m,5H),2.01(dd,J=13.0,6.8Hz,1H),1.88(s,3H),1.81(s,6H),1.75-1.56(m,4H),1.30-1.03(m,4H),0.60(d,J=6.9Hz,3H),0.54(d,J=8.5Hz,1H),0.33(s,18H).Anal.Calcd.forC45H65MgN3OSi2:C,72.60;H,8.80;N,5.64.Found:C,72.04;H,8.76;N,5.23%.
实施例27
镁络合物Mg5的合成
在氩气保护下,于50mLSchlenk瓶内加入Mg[N(SiMe3)2]2(0.520g,1.50mmol),3mL甲苯,再慢慢加入配体L5(0.632g,1.50mmol)的甲苯溶液,室温搅拌,析出白色固体,过滤,抽去溶剂得白色固体Mg5(0.550g,产率:60.6%),两种异构体,比例为2∶1。
1HNMR(400MHz,C6D6):δ7.44(d,J=2.7Hz,1H),7.19-7.16(m,3H),7.11(t,J=6.0Hz,2H),6.55(d,J=2.7Hz,1H),3.95(d,J=13.1Hz,1H),3.86(d,J=13.4Hz,1H),3.60(d,J=12.9Hz,1H),3.41(d,J=13.5Hz,1H),2.57-2.47(m,1H),2.42(dd,J=11.3,5.6Hz,2H),2.28(td,J=11.9,3.9Hz,1H),2.03(ddd,J=35.5,22.1,11.5Hz,2H),1.91-1.76(m,3H),1.39-1.29(m,1H),1.14(td,J=15.0,7.6Hz,2H),0.99(d,J=7.2Hz,3H),0.52(s,18H).Anal.Calcd.forC29H47Cl2MgN3OSi2:C,57.56;H,7.83;N,6.94.Found:C,57.39;H,7.55;N,6.66%.
实施例28
镁络合物Mg7的合成
在氩气保护下,于50mLSchlenk瓶内加入Mg[N(SiMe3)2]2(0.520g,1.50mmol),3mL甲苯,再慢慢加入配体L7(0.912g,1.50mmol)的甲苯溶液,室温搅拌,用甲苯和正己烷重结晶,得白色固体Mg7(0.508g,产率:42.8%)。
1HNMR(400MHz,C6D6):δ7.58(dd,J=61.5,24.1Hz,7H),7.27(d,J=2.1Hz,1H),7.14-7.08(m,8H),7.03-6.90(m,6H),6.52(d,J=2.2Hz,1H),4.38(d,J=12.9Hz,1H),4.21(d,J=14.2Hz,1H),4.13(d,J=14.0Hz,1H),3.43(d,J=13.1Hz,1H),3.22(dd,J=12.6,6.4Hz,1H),,2.06(s,3H),2.01-1.88(m,2H),1.73(dd,J=14.0,3.7Hz,1H),1.51(qd,J=13.4,9.7Hz,2H),1.36-1.26(m,3H),1.11-0.99(m,2H),0.93(t,J=7.2Hz,3H),0.80-0.70(m,1H),0.50-0.40(m,1H),0.30(s,18H).Anal.Calcd.forC49H65MgN3OSi2:C,74.26;H,8.27;N,5.30.Found:C,73.96;H,8.54;N,5.04%.
实施例29
镁络合物Mg12的合成
在氩气保护下,于50mLSchlenk瓶内加入Mg[N(SiMe3)2]2(0.520g,1.50mmol),3mL甲苯,再慢慢加入配体L12(0.912g,1.50mmol)的甲苯溶液,室温搅拌,用甲苯和正己烷重结晶,得白色固体Mg12(0.531g,产率:44.7%)。
1HNMR(400MHz,C6D6):δ7.58(dd,J=61.5,24.1Hz,7H),7.27(d,J=2.1Hz,1H),7.14-7.08(m,8H),7.03-6.90(m,6H),6.52(d,J=2.2Hz,1H),4.38(d,J=12.9Hz,1H),4.21(d,J=14.2Hz,1H),4.13(d,J=14.0Hz,1H),3.43(d,J=13.1Hz,1H),3.22(dd,J=12.6,6.4Hz,1H),,2.06(s,3H),2.01-1.88(m,2H),1.73(dd,J=14.0,3.7Hz,1H),1.51(qd,J=13.4,9.7Hz,2H),1.36-1.26(m,3H),1.11-0.99(m,2H),0.93(t,J=7.2Hz,3H),0.80-0.70(m,1H),0.50-0.40(m,1H),0.30(s,18H).Anal.Calcd.forC49H65MgN3OSi2:C,74.26;H,8.27;N,5.30.Found:C,74.13;H,8.29;N,5.24%.
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),用0.5mL甲苯溶解。量取催化剂Zn1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应30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:97%,Mn=3.1×104g/mol,分子量分布PDI=1.79,规整度Pm=0.39。
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),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应5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:99%,Mn=1.8×104g/mol,分子量分布PDI=1.53,规整度Pm=0.39。
实施例32
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.216g,1.50mmol),用1.4mL甲苯溶解,加入0.02mL异丙醇甲苯溶液。量取催化剂Zn1的甲苯溶液0.1mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.00066M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶1500。控制反应温度25℃,反应20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:96%,Mn=1.1×105g/mol,分子量分布PDI=1.13,规整度Pm=0.39。
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),用0.5mL四氢呋喃溶解。量取催化剂Zn1的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应20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:96%,Mn=1.7×105g/mol,分子量分布PDI=1.54,规整度Pm=0.51。
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),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Zn1的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应5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:99%,Mn=2.7×104g/mol,分子量分布PDI=1.49,规整度Pm=0.53。
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),用0.5mL甲苯溶解。量取催化剂Zn2的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应30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:91%,Mn=5.7×104g/mol,分子量分布PDI=1.59,规整度Pm=0.70。
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),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn2的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应15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:99%,Mn=2.6×104g/mol,分子量分布PDI=1.33,规整度Pm=0.70。
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),用0.5mL四氢呋喃溶解。量取催化剂Zn2的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应30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:96%,Mn=4.5×105g/mol,分子量分布PDI=1.61,规整度Pm=0.71。
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),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Zn2的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应30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:99%,Mn=2.6×104g/mol,分子量分布PDI=1.53,规整度Pm=0.70。
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),用0.5mL甲苯溶解。量取催化剂Zn3的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应1小时,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:98%,Mn=2.4×104g/mol,分子量分布PDI=1.74,规整度Pm=0.71。
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),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn3的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应20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:99%,Mn=1.7×104g/mol,分子量分布PDI=1.36,规整度Pm=0.71。
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),用0.5mL甲苯溶解。量取催化剂Zn4的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应7小时,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:86%,Mn=1.3×105g/mol,分子量分布PDI=1.47,规整度Pm=0.75。
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),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn4的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应1.5小时,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:93%,Mn=3.7×104g/mol,分子量分布PDI=1.08,规整度Pm=0.75,Tm=150℃。
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),用0.5mL四氢呋喃溶解。量取催化剂Zn4的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应5小时,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:94%,Mn=7.4×104g/mol,分子量分布PDI=1.40,规整度Pm=0.75,Tm=150℃。
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),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Zn4的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应1小时,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:84%,Mn=2.3×104g/mol,分子量分布PDI=1.15,规整度Pm=0.75,Tm=150℃。
实施例45
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn7的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应3小时,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:84%,Mn=2.9×104g/mol,分子量分布PDI=1.66,规整度Pm=0.78,Tm=156℃。
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),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn7的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应1.5小时,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:95%,Mn=3.7×104g/mol,分子量分布PDI=1.22,规整度Pm=0.77,Tm=156℃。
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),用0.5mL四氢呋喃溶解。量取催化剂Zn7的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应5小时,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:75%,Mn=9.1×104g/mol,分子量分布PDI=1.25,规整度Pm=0.76,Tm=156℃。
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),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Zn7的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应3小时,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:86%,Mn=3.3×104g/mol,分子量分布PDI=1.09,规整度Pm=0.77,Tm=156℃。
实施例45
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn7的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度-38℃,反应7天,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:66%,规整度Pm=0.84,Tm=169℃。
实施例46
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Zn7的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度-38℃,反应5天,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:96%,Mn=4.2×104g/mol,分子量分布PDI=1.4,规整度Pm=0.84,Tm=168℃。
实施例47
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn8的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应20小时,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%,Mn=5.9×104g/mol,分子量分布PDI=1.60,规整度Pm=0.75。
实施例48
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn8的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应1.5小时,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:94%,Mn=3.1×104g/mol,分子量分布PDI=1.09,规整度Pm=0.76。
实施例49
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn9的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应3小时,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:99%,Mn=3.7×104g/mol,分子量分布PDI=1.13,规整度Pm=0.70。
实施例50
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn11的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应3小时,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:88%,Mn=8.1×104g/mol,分子量分布PDI=1.16,规整度Pm=0.77。
实施例51
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn11的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应2小时,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%,Mn=3.3×104g/mol,分子量分布PDI=1.06,规整度Pm=0.76。
实施例52
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn12的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应3.5小时,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:93%,Mn=8.3×104g/mol,分子量分布PDI=1.72,规整度Pm=0.78。
实施例53
氩气保护下,在聚合瓶中加入L-丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn12的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应半小时,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:95%,Mn=3.6×104g/mol,分子量分布PDI=1.36。
实施例54
氩气保护下,在聚合瓶中加入D-丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn12的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应2小时,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:94%,Mn=4.3×104g/mol,分子量分布PDI=1.42。
实施例55
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn12的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应0.5小时,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:96%,Mn=4.2×104g/mol,分子量分布PDI=1.35,规整度Pm=0.77。
实施例56
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。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=0.005M,[Mg]0∶[rac-LA]0=1∶200。控制反应温度25℃,反应10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%,Mn=4.7×104g/mol,分子量分布PDI=1.41,规整度Pm=0.47。
实施例57
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。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=0.005M,[Mg]0∶[iPrOH]0∶[rac-LA]0=1∶1∶200。控制反应温度25℃,反应0.5小时,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:95%,Mn=3.3×104g/mol,分子量分布PDI=1.12,规整度Pm=0.45。
实施例58
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。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∶[rac-LA]0=1∶200。控制反应温度25℃,反应0.5小时,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:96%,Mn=5.1×104g/mol,分子量分布PDI=1.31,规整度Pr=0.72。
实施例59
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。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10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:95%,Mn=2.7×104g/mol,分子量分布PDI=1.16,规整度Pr=0.73。
实施例60
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg7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∶[rac-LA]0=1∶200。控制反应温度25℃,反应0.5小时,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:93%,Mn=5.6×104g/mol,分子量分布PDI=1.49,规整度Pr=0.76。
实施例61
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Mg7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10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:96%,Mn=3.4×104g/mol,分子量分布PDI=1.23,规整度Pr=0.75。
实施例62
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg7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∶[rac-LA]0=1∶200。控制反应温度-38℃,反应4天,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:93%,Mn=7.2×104g/mol,分子量分布PDI=1.59,规整度Pr=0.84。
实施例63
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Mg7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-38℃,反应2天,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:91%,Mn=3.6×104g/mol,分子量分布PDI=1.33,规整度Pr=0.83。
实施例64
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL四氢呋喃溶解。量取催化剂Mg7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20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:96%,Mn=4.8×104g/mol,分子量分布PDI=1.54,规整度Pr=0.66。
实施例65
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Mg7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10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%,Mn=2.4×104g/mol,分子量分布PDI=1.18,规整度Pr=0.65。
实施例66
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL四氢呋喃溶解。量取催化剂Mg7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-38℃,反应3天,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:82%,Mn=5.1×104g/mol,分子量分布PDI=1.49,规整度Pr=0.73。
实施例67
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg12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∶[rac-LA]0=1∶200。控制反应温度25℃,反应0.5小时,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:94%,Mn=4.9×104g/mol,分子量分布PDI=1.45,规整度Pr=0.76。
实施例68
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Mg12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10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:97%,Mn=3.3×104g/mol,分子量分布PDI=1.26,规整度Pr=0.75。
实施例69
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg12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∶[rac-LA]0=1∶200。控制反应温度-38℃,反应4天,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:85%,Mn=4.2×104g/mol,分子量分布PDI=1.50,规整度Pr=0.84。
实施例70
氩气保护下,在聚合瓶中加入L-丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg12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∶[rac-LA]0=1∶200。控制反应温度25℃,反应20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:98%,Mn=4.1×104g/mol,分子量分布PDI=1.42。
实施例71
氩气保护下,在聚合瓶中加入D-丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg12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∶[rac-LA]0=1∶200。控制反应温度25℃,反应20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:97%,Mn=3.9×104g/mol,分子量分布PDI=1.46。
实施例72
氩气保护下,在聚合瓶中加入β-丁内酯(0.086g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[rac-BBL]0=1∶200。控制反应温度25℃,反应24小时,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:95%,Mn=3.2×104g/mol,分子量分布PDI=1.44。
实施例73
氩气保护下,在聚合瓶中加入β-丁内酯(0.086g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0∶[iPrOH]0∶[rac-BBL]0=1∶1∶200。控制反应温度25℃,反应12小时,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:91%,Mn=1.4×104g/mol,分子量分布PDI=1.14。
Claims (10)
1.一种手性胺基酚类配体(I)及其金属锌、镁化合物(II),其特征在于,具有以下通式:
式(I)、(II)中:
R1~R4分别代表C1~C20直链、支链结构的烷基,C7~C30单或多芳基取代的烷基;
R5代表胺基NR6R7,其中R6~R7分别为三甲基硅基,三乙基硅基,二甲基氢硅基,R6和R7可以相同或不同;
M代表锌、镁。
2.根据权利要求1所述的手性胺基酚类配体(I)及其金属锌、镁化合物(II),其特征在于,R1~R4为C1~C8直链、支链结构的烷基,C7~C20单或多芳基取代的烷基;R5代表二(三甲基硅)胺基,二(三乙基硅)胺基,二(二甲基氢硅)胺基。
3.根据权利要求1所述的手性胺基酚类配体(I)及其金属锌、镁化合物(II),其特征在于,R1~R2优选为甲基、异丙基、叔丁基、枯基、三苯甲基;R3优选为甲基、乙基、异丙基、正丁基、正辛基、苄基;R4优选为甲基、异丙基、苄基、(1-萘基)甲基;R5优选为二(三甲基硅)胺基。
4.权利要求1~3任一项所述的手性胺基酚类配体(I)及其金属锌、镁化合物(II)的制备方法,包括如下步骤:
将式(III)所示的手性N-取代-2-氨基甲基四氢吡咯与取代醛O=CH-R4发生西佛碱反应生成亚胺,再加入还原剂还原成仲胺后,加入取代酚(IV)和多聚甲醛,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化合物(I);
任选的,再将式(I)所示的手性胺基酚类配体化合物与锌或镁的金属原料化合物在有机介质中反应,生成手性胺基酚氧基锌或镁化合物,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化合物(II);
反应式中取代基R1~R5与权利要求1~3任一项所述的手性胺基酚类配体(I)及其金属锌、镁化合物(II)的各相应基团一致。
5.根据权利要求4所述的方法,其特征在于,还原剂优选氢化铝锂或硼氢化钠;锌或镁的金属原料化合物优选二{二(三甲基硅)胺基}锌、二{二(三甲基硅)胺基}镁;手性胺基酚类配体化合物与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任一项所述的手性胺基酚氧基锌或镁化合物的应用,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任一项所述的手性胺基酚氧基锌或镁化合物为催化剂,使丙交酯在-39~130℃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任一项所述的手性胺基酚氧基锌或镁化合物为催化剂,在醇存在的条件下,使丙交酯在-39~130℃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任一项所述的手性胺基酚氧基锌或镁化合物为催化剂,在醇存在下或不加醇,使β-丁内酯在-39~50℃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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CN109879801A (zh) * | 2019-03-25 | 2019-06-14 | 华东理工大学 | 一种含吡啶环的氨基酚氧基锌络合物及其制备方法和应用 |
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