CN104557874B - 喹啉胺基吲哚基锌、镁、钙化合物及其制备方法和应用 - Google Patents
喹啉胺基吲哚基锌、镁、钙化合物及其制备方法和应用 Download PDFInfo
- Publication number
- CN104557874B CN104557874B CN201410789188.2A CN201410789188A CN104557874B CN 104557874 B CN104557874 B CN 104557874B CN 201410789188 A CN201410789188 A CN 201410789188A CN 104557874 B CN104557874 B CN 104557874B
- Authority
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- China
- Prior art keywords
- magnesium
- zinc
- amido
- formula
- quinoline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000011701 zinc Substances 0.000 title claims abstract description 91
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 73
- 239000011777 magnesium Substances 0.000 title claims abstract description 71
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 62
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 58
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 150000001674 calcium compounds Chemical class 0.000 title claims abstract description 31
- 229940043430 calcium compound Drugs 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000003368 amide group Chemical group 0.000 claims abstract description 43
- 239000003446 ligand Substances 0.000 claims abstract description 37
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 14
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 239000011575 calcium Chemical group 0.000 claims description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 33
- 229910052791 calcium Inorganic materials 0.000 claims description 33
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 31
- -1 bromomethyl compound Chemical class 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- 230000004044 response Effects 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 7
- 229960004217 benzyl alcohol Drugs 0.000 claims description 7
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 6
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000002585 base Substances 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
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- GAMXENREBLKBNY-UHFFFAOYSA-N O1CCCC1.[Ca] Chemical compound O1CCCC1.[Ca] GAMXENREBLKBNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 2
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 125000005997 bromomethyl group Chemical group 0.000 claims 1
- 230000002308 calcification Effects 0.000 claims 1
- 150000002475 indoles Chemical class 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 43
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 13
- 239000004626 polylactic acid Substances 0.000 abstract description 11
- 238000001953 recrystallisation Methods 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 150000002596 lactones Chemical group 0.000 abstract description 8
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 239000002685 polymerization catalyst Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 44
- 238000003786 synthesis reaction Methods 0.000 description 44
- 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 34
- 238000005160 1H NMR spectroscopy Methods 0.000 description 31
- 239000000243 solution Substances 0.000 description 31
- 239000007787 solid Substances 0.000 description 27
- 239000002904 solvent Substances 0.000 description 26
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000011017 operating method Methods 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
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- 239000000284 extract Substances 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
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- CMVPIVAWAQZQKP-UHFFFAOYSA-N tert-butyl 2-methylindole-1-carboxylate Chemical class C1=CC=C2N(C(=O)OC(C)(C)C)C(C)=CC2=C1 CMVPIVAWAQZQKP-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
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- 241000239226 Scorpiones Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
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- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PRKHIUMROXYMTB-UHFFFAOYSA-N tert-butyl 3-bromo-2-(bromomethyl)indole-1-carboxylate Chemical compound C1=CC=C2N(C(=O)OC(C)(C)C)C(CBr)=C(Br)C2=C1 PRKHIUMROXYMTB-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-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
- NNAYPIDFVQLEDK-UHFFFAOYSA-N 2-(bromomethyl)quinoline Chemical compound C1=CC=CC2=NC(CBr)=CC=C21 NNAYPIDFVQLEDK-UHFFFAOYSA-N 0.000 description 1
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- IAAUGSYGHOFWEW-UHFFFAOYSA-N 8-(bromomethyl)quinoline Chemical compound C1=CN=C2C(CBr)=CC=CC2=C1 IAAUGSYGHOFWEW-UHFFFAOYSA-N 0.000 description 1
- MDEYYYUXVRDMPL-UHFFFAOYSA-N 8-propan-2-ylquinoline-2-carbaldehyde Chemical compound C1=C(C=O)N=C2C(C(C)C)=CC=CC2=C1 MDEYYYUXVRDMPL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种喹啉取代胺基吲哚基锌、镁、钙化合物及其制备方法和在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,让后经过滤、抽干、重结晶步骤获得目标化合物。本发明的喹啉取代胺基吲哚基锌、镁、钙化合物是高效的内酯开环聚合催化剂,可用于催化丙交酯、ε‑己内酯、β‑丁内酯、α‑甲基(三亚甲基碳酸酯)等的聚合反应;特别对于外消旋丙交酯可以得到中等杂规度的聚乳酸。本发明的喹啉取代胺基吲哚基锌、镁、钙化合物的优点十分明显:原料易得,合成路线简单,目标产物收率高,具有较高的催化活性,能获得高分子量及窄分子量分布的聚丙交酯,能够满足工业部门的需要。其结构式如下所示:
Description
技术领域
本发明涉及一类喹啉取代胺基吲哚基锌、镁、钙化合物,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聚烯烃高分子材料的聚合物,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,通过催化剂引发乳酸二聚体——丙交酯开环聚合制备聚乳酸,在分子量及聚合物微观链结构方面具有高度可控性,从而可实现有效控制所得聚乳酸的性能;原料造价较低的丙交酯通过与其他单体共聚更可以得到多种新型结构性能的聚合物。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)。不同丙交酯单体通过金属络合物催化剂催化可以制得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、嵌段等规聚乳酸以及等规聚乳酸立体复合物。结构明确、具单一引发基团的金属络合物(通式:LnMX,Ln是一个或多个多齿配体;M为中心金属;X是引发基团)通常能有效地引发丙交酯开环聚合,精确控制聚合速率、所得聚合物分子量及分子量分布以及共聚单体的有效插入,同时也是表现出立体选择性最多的一类催化剂(Polym.Chem.,2011,2,520–527)。其中,锌、镁、钙作为人体必需元素,其无色无毒以及具有生物相容性等特点使得相应金属络合物作为催化剂更符合聚乳酸在食品包装及医药领域的应用要求。因此,开发含单阴离子配体的锌、镁、钙络合物催化剂(LM2+X)成为该领域广泛关注的研究热点(Dalton Trans.,2009,4832–4846)。
随着锌、镁、钙金属共价半径(Zn:1.21;Mg:1.41;Ca:)的不断增大,结构稳定的LM2+X型络合物数量显著减少,更易通过Schlenk平衡副反应得到均配型络合物L2M和MX2,从而大大降低了催化剂的催化性能。此外,能同时稳定锌、镁、钙金属中心的多齿配体结构数量更为有限。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分别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)。然而,在合成相同配体钙络合物(BDI)CaX时, 仅X基团为大位阻硅胺基的络合物如(BDI)CaN(SiMe3)2能稳定存在;合成X基团为烷氧基络合物(X=OiPr或OtBu)时发生Schlenk平衡反应得到以均配络合物为主的混合物。2004年,Chisholm等人合成了三吡唑硼[NNN]三齿配位的锌、镁、钙络合物,其中钙络合物对外消旋丙交酯开环聚合表现出很高的催化活性(1min,>90%conv.)和高杂规选择性(Pr=0.9)(Inorg.Chem.,2004,43,6717–6725)。Lin小组(Macromolecules,2006,39,3745–3752)和Darensbourg小组(Inorg.Chem.,2009,48,728–734)分别报道了希夫碱配体的锌、镁和钙络合物,研究其位阻、电子效应和温度对聚合物规整度的影响,其均配钙络合物(polymer,2007,48,2257–2262)本身对丙交酯没有催化活性,在两当量BnOH存在下才表现出中等活性(1h,96%conv.)。2009年,Sarazin和Carpentier小组报道了含吗啡啉基的胺基酚氧基锌、镁、钙络合物催化丙交酯开环聚合表现出“不死聚合”的特征。其中钙络合物在加入10–50当量醇的条件下,15min内可以使1000当量单体顺利聚合,且所得聚合物分子量分布相对较窄(Dalton Trans.,2009,9820–9827)。2012年,Carpentier小组将吗啡啉基团换成冠醚,并引入三氟甲基改变电子效应,合成了一系列锌和碱土金属的硅胺基络合物,证明了在固体状态下和溶液中,M···F和M···Si–H作用的存在有利于稳定金属半径较大的钙、锶、钡络合物(J.Am.Chem.Soc.,2011,133,9069–9087;Chem.–Eur.J.,2012,18,6289–6301)。
到目前为止,锌、镁、钙等络合物作为内酯开环聚合催化剂,对外消旋丙交酯只表现出了较高的杂规选择性,近两年才出现了几例锌金属络合物表现出中等到高等规选择性的报道。本组于2013年报道了一系列手性胺基酚氧基锌络合物催化外消旋丙交酯开环聚合,首次获得了集较高活性和等规选择性(Pm=0.84)的金属锌络合物催化剂(Chem.Commun.,2013,49,8686–8688)。2013年,Otero报道了含有茂配体的手性杂异蝎型锌络合物,尽管催化外消旋丙交酯聚合活性较低,但得到中等程度等规聚合物(Pm=0.77)(Organometallics,2013,32,3437–3440)。Du小组于2014年报道了一系列基于邻位取代手性噁唑衍生的类β-二亚胺配体的锌络合物,这类锌络合物对外消旋丙交酯聚合在高温条件下具有较高的活性,得到了等规度为Pm=0.77-0.91的多嵌段等规聚丙交酯(ACS Macro Lett.,2014,3,689–692.)。崔冬梅小组在2014年报道了一类非手性膦亚胺取代的杂异蝎型阴阳离子型锌络合物,催化外消旋丙交酯聚合时可以得到较高等规度聚丙交酯(Pm=0.68-0.85)(Chem.Commun.,2014,50,11411–11414)。
综上所述,尽管具单一引发基团的杂配型金属锌、镁、钙络合物在催化丙交酯开环聚合中已表现出较高的活性和立体选择性。但是,能同时稳定金属锌、镁、钙络合物的配体结构报道较少、取代基可变性不大(只有少量大位阻的钙络合物能稳定存在),镁与钙络合物没有表现出明显的等规选择性。其中,钙络合物的合成和应用更是受到了多方面的限制:(i)对 空气和水高度敏感;(ii)原子半径大,Ca2+电正性强;(iii)溶解性差,难溶于常见有机溶剂;(iv)倾向于发生Schlenk平衡生成无活性的均配络合物。因此,设计合成新型配体结构的锌、镁、钙络合物,用于催化内酯开环聚合的研究工作有待于进一步开展,以期获得集高稳定性、高活性、高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喹啉取代胺基吲哚基锌、镁、钙化合物。
本发明目的之二在于公开喹啉取代胺基吲哚基锌、镁、钙化合物的制备方法。
本发明目的之三在于公开喹啉取代胺基吲哚基锌、镁、钙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,已证实锌络合物催化外消旋丙交酯获得杂规聚乳酸是链端机理控制(J.Am.Chem.Soc.,2001,123,3229),而最近报道的几例手性或非手性锌络合物表现出中等到较高等规选择性,其中手性中心控制和链端控制分别或同时存在。配体对称性、手性与络合物立体选择性之间的联系尚不清晰。此外,该领域的传统配体结构多以二齿、三齿的酚胺、酚亚胺及其衍生物为主,催化过程中金属活性物种之间容易发生桥联、团聚或重新组合。因此,本发明所设计的配体为四齿喹啉取代胺基吲哚类化合物,以期用于与锌、镁、钙络合物得到类C3对称的金属络合物。多齿配位使催化剂在引发期和增长期均保持单核活性中心,聚合过程中诱导手性丙交酯单体与金属选择性配位开环,达到催化外消旋丙交酯立体选择性开环聚合的目的。此外,在类C3对称骨架基础上,进一步引入手性或改变其上各相关取代基,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。
本发明提供的喹啉取代胺基吲哚类配体(I)及其金属锌、镁、钙化合物(II),其特征在于,具有以下通式:
式(I)和(II)中:
R1代表氢,卤素;R1优选氢,溴;
R2代表氢,C1~C10直链、支链结构的烷基;更为特征的,R2为氢,C1~C6直链、支链结 构的烷基;R2优选为氢、甲基、正丁基;
A1和A2为具有如式(III)或式(IV)所示结构的基团:
A1和A2同时为结构(III)或结构(IV)所示基团;A1和A2为式(IV)所示基团时,两者可以相同或不同;式(IV)中,R3代表氢,C1~C10直链、支链结构的烷基;更为特征的,R3为C1~C6直链、支链结构的烷基;R3优选为氢、异丙基;
式(II)中A1和A2通过其氮原子与金属M中心配位;A1和A2同时或不同时与金属中心配位;虚线代表A1和A2与金属之间可能成键、有弱作用、或不成键。
M代表锌、镁、钙;
X代表C1~C6直链、支链结构的烷基,C1~C6直链、支链结构的烷氧基,二(三甲基硅基)胺基,二(二甲基硅基)胺基;更为特征的,X为C1~C4直链、支链结构的烷基,C1~C4直链、支链结构的烷氧基,二(三甲基硅基)胺基,二(二甲基硅基)胺基;X优选为乙基、叔丁氧基、二(三甲基硅)胺基、二(二甲基硅)胺基。
优选的喹啉取代胺基吲哚类配体,其结构式如下:
优选的喹啉取代胺基吲哚类配体的金属锌、镁、钙化合物结构为:
本发明所述的喹啉取代胺基吲哚类配体(I)及其金属锌、镁、钙化合物(II)的制备方法,包括如下步骤:
当A1与A2相同时,将式(V)所示取代1H-吲哚-2-烷基胺与式(VI)和式(VII)所示含A1或A2基团的溴甲基化合物发生亲核取代反应,以三乙胺作缚酸剂脱除生成的氢溴酸; 反应温度为25~50℃,反应时间为24~72小时,然后从反应产物中收集化合物(I);
当A1与A2不同时,将式(V)所示取代1H-吲哚-2-烷基胺先与式(VI)所示含A1基团的溴甲基化合物发生第一次亲核取代反应,以三乙胺作缚酸剂脱除生成的氢溴酸,反应温度为25~50℃,反应时间为24~72小时;再向反应液中加入式(VII)所示含A2基团的溴甲基化合物发生第二次亲核取代反应,反应温度为25~50℃,反应时间为24~72小时,然后从反应产物中收集化合物(I);
任选的,将式(I)所示喹啉取代胺基吲哚类配体化合物与锌、镁或钙的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12~96小时,然后从反应产物中收集目标喹啉取代胺基吲哚基锌、镁或钙化合物(II);
任选的,将式(I)所示喹啉取代胺基吲哚类配体化合物与锌、镁或钙的金属原料化合物在有机介质中反应,之后再加入C1~C6直链或支链结构的醇继续反应,反应温度为0~100℃,反应时间为12~96小时,然后从反应产物中收集目标喹啉取代胺基吲哚基锌、镁或钙化合物(II)。
上述制备方法中式(V)、(VI)、(VII)中取代基R1、R2、A1和A2与满足本发明的喹啉取代胺基吲哚类配体(I)及其金属锌、镁、钙化合物(II)的各相应基团的要求一致;
金属原料化合物具有通式MX2(THF),M=Zn、Mg、Ca;n=0,2;X代表C1~C6直链、支链结构的烷基,二(三甲基硅基)胺基,二(二甲基硅基)胺基;金属原料化合物优选为二乙基锌、二正丁基镁、二{二(三甲基硅基)胺基}锌、二{二(三甲基硅基)胺基}镁、二{二(三甲基硅基)胺基}二(四氢呋喃)钙、二{二(二甲基硅基)胺基}二(四氢呋喃)钙;
喹啉取代胺基吲哚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。
本发明所述喹啉取代胺基吲哚类配体化合物(I)的制备方法中,式(V)所示取代1H-吲哚-2-烷基胺的合成可参考文献方法按以下路线进行合成:
R2=烷基时
当R2=H时,式(IX)所示的3位取代N-Boc-2-甲基-1H-吲哚与一当量溴代丁二酰亚胺(NBS)在四氯化碳中发生自由基反应生成式(VIII)所示的3位取代N-Boc-2-溴甲基-1H-吲哚(Eur.J.Org.Chem.2004,3484–3496);再利用Gabriel合成胺方法制备目标化合物(V)(Gabriel,S.Ber.Dtsch.Chem.Ges.1887,20,2224;Chem–Eur.J.,2010,16,10171–10177)。
当R2=烷基时,将式(XII)所示的3位取代1H-吲哚-2-甲酸与烷基锂试剂发生亲核取代反应生成酮(XI),继续与羟胺反应生成酮肟(X),酮肟被氢化铝锂还原得到目标化合物(V)(Bioorg.Med.Chem.,1998,6,1759–1763)。
原料式(IX)所示3位取代取代N-Boc-2-甲基-1H-吲哚可购买或参照已知文献合成获得(R1=Cl:J.Chem.Res.(S),1989,182–183;Br:Tetrahedron Lett.,1986,27,1051–1054;I:Chin.Chem.Lett.,2012,23,1230–1232;)。当R1=H时,原料式(VIII)所示化合物可参照已知文献合成(J.Med.Chem.,2006,49,7108–7118)。
本发明所述喹啉取代胺基吲哚类配体化合物(I)的制备方法中,A1和A2同为结构(IV)所示基团时,式(VI)或式(VII)所示含A1或A2基团的溴甲基化合物,即8位取代-2-溴甲基喹啉化合物可参考文献方法按以下路线进行合成:
将式(XV)所示邻位取代苯胺与反式丁烯醛在酸催化下发生Doebner-von Miller反应生成式(XIV)所示8位取代2-甲基喹啉化合物(Ber.Dtsch.Chem.Ges.,1883,16,2464;喹啉衍生物的制备方法.中国.102134219[P].2011-07-27)。式(XIV)所示化合物被二氧化硒氧化成8位取代喹啉-2-甲醛、之后被NaBH4还原成式(XIII)所示8位取代喹啉-2-甲醇(Chem.Mater.,2010,22,2114–2119)。式(XIII)所示8位取代喹啉-2-甲醇化合物与甲磺酰氯反应生成甲磺 酸酯,继续与无水溴化锂反应生成式(VI)或式(VII)所示目标化合物(Synthesis,1994,1181–1184)。
本发明提供的锌、镁、钙化合物是一种高效的内酯开环聚合催化剂,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。
以本发明喹啉取代胺基吲哚基锌、镁、钙化合物为催化剂,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。
以本发明喹啉取代胺基吲哚基锌、镁、钙化合物为催化剂,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的摩尔比为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。
以本发明喹啉取代胺基吲哚基锌、镁、钙化合物为催化剂,在醇存在下或不加醇,使ε-己内酯在-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。
以本发明喹啉取代胺基吲哚基锌、镁、钙化合物为催化剂,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。
以本发明喹啉取代胺基吲哚基锌、镁、钙化合物为催化剂,在醇存在下或不加醇,使α-甲基(三亚甲基碳酸酯)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。
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中等程度的立体选择性,易获得高分子量及窄分布的聚内酯。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L1的合成:
(1)(3-溴-1H-吲哚-2-)甲胺的合成
1)N-Boc-3-溴-2-溴甲基吲哚的合成
(方法一)
用50mL四氯化碳溶解N-Boc-2-甲基吲哚(7.51g,32.5mmol)、溴代丁二酰亚胺(11.56 g,65.0mmol)和过氧苯甲酰(0.079g,0.325mmol),85℃回流12h后,停止加热,静置冷却,过滤除去丁二酰亚胺,滤液浓缩,重结晶得淡黄色针状晶体(9.80g,77.5%)。1H NMR(400MHz,CDCl3):δ8.19(d,1H,3J=8.4Hz),7.53(d,1H,3J=7.8Hz),7.40(dd,1H,3J=11.6,4J=4.2Hz),7.32(t,1H,3J=7.6Hz),5.07(s,2H),1.74(s,9H).
(方法二)
四氯化碳溶解N-Boc-2-甲基-3-溴吲哚(3.10g,10.0mmol)、溴代丁二酰亚胺(1.78g,10mmol)和过氧苯甲酰(0.04g,0.168mmol),85℃回流12h后,停止加热,静置冷却,过滤除去丁二酰亚胺,滤液浓缩,重结晶得淡黄色针状晶体(3.6g,92.5%)。
2)N-(3-溴-1H-吲哚-2-甲基)-邻苯二甲酰亚胺的合成
用70mL N,N-二甲基甲酰胺溶解N-Boc-3-溴-2-溴甲基吲哚(9.80g,25.2mmol)和邻苯二甲酰亚胺钾盐(4.67g,25.2mmol),145℃回流2h。抽除溶剂得棕色固体,甲醇重结晶得无色晶体(7.53g,84.1%)。1H NMR(CDCl3,400MHz):δ9.03(s,1H),7.85(dd,2H,3J=5.6,3J=3.2Hz),7.72(dd,2H,3J=5.6,3J=3.2Hz),7.56-7.48(m,1H),7.35-7.29(m,1H),7.22(ddd,1H,
3J=8.2Hz,3J=6.8Hz,4J=1.2Hz),7.15(ddd,1H,3J=8.2Hz,3J=6.8Hz,4J=1.2Hz),5.09(s,1H).
3)(3-溴-1H-吲哚-2-)甲胺的合成
用250mL无水乙醇溶解N-(3-溴-1H-吲哚-2-甲基)-邻苯二甲酰亚胺(7.53g)和80%wt.水合肼(4.29g,68.6mmol),90℃回流48h,静置冷却,过滤,滤液浓缩重结晶得棕色固体(3.40g,产率71.2%)。1H NMR(CDCl3,400MHz):δ9.32(s,1H),7.51(dd,1H,3J=6.8Hz,4J=1.6Hz),7.31(dd,1H,3J=7.2Hz,4J=1.2Hz),7.20(td,1H,3J=6.8Hz,4J=1.2Hz),7.16(td,1H,3J=6.8Hz,4J=1.2Hz),4.07(s,2H),2.29(br,2H).Mp:℃:99.6-101.3℃.
(2)配体L1的合成
向8-溴甲基喹啉(2.78g,12.2mmol)的20mL四氢呋喃溶液中,滴加(3-溴-1H-吲哚基-2-)甲胺(1.37g,6.08mmol)和三乙胺(1.54g,15.2mmol)的20mL四氢呋喃溶液,室温搅拌3天。旋转蒸发除去溶剂得棕色粘稠物。柱层析分离(200~300目硅胶;石油醚:乙酸乙酯=20:1~5:1),得黄色粘稠油状物,四氢呋喃和石油醚混合溶剂重结晶得浅黄色晶体(2.00g,产率为64.8%)。1H NMR(400MHz,CDCl3):δ13.50(s,1H),9.12(dd,2H,3J=4.2Hz,4J=1.7Hz,),8.16(dd,2H,3J=8.2Hz,4J=1.7Hz),7.78(d,2H,3J=7.0Hz),7.65(dd,2H,3J=4.0Hz,4J=0.8Hz),7.64(d,1H,3J=7.6Hz),7.55(d,1H,3J=7.8Hz),7.48(dd,2H,3J=8.2Hz,4J=4.2Hz),7.40-7.36(m,2H),7.26(td,1H,3J=7.6Hz,4J=0.8Hz),7.18(td,1H,3J=7.4Hz,4J=0.8Hz),4.46(s,4H),4.05(s,2H).13C NMR(100MHz,CDCl3):δ155.9,148.7,146.7,137.2,136.6,130.7,128.6,127.5,126.5,121.6,121.1,55.4,53.7.Anal.Calcd.for C29H23BrN4·(0.05CH2Cl2):C,68.37;H,4.56;N,10.99;Found:C,68.03;H,4.7;N,10.87%.
实施例2
配体L2的合成
除原料采用2-溴甲基喹啉(6.21g,28.0mmol)、(3-溴-1H-吲哚基-2-)甲胺(3.15g,14.0mmol)外,其他操作步骤同实施例1。重结晶得浅黄色晶体(2.00g,产率为28.2%)。1H NMR(400MHz,CDCl3):δ11.75(s,1H),8.18(d,2H,3J=8.4Hz),8.11(dd,2H,3J=8.4Hz,4J=1.6Hz),7.80(d,2H,3J=8.0Hz),7.77-7.73(m,2H),7.57-7.53(m,6H),7.24(td,1H,3J=8.0Hz,4J=1.2Hz),7.18(td,1H,3J=7.2Hz,4J=0.8Hz),4.10(s,4H),4.00(s,2H).13C NMR(100MHz,CDCl3):δ159.5,147.5,136.9,135.2,133.0,129.8,128.9,127.8,127.6,127.5,126.60,122.5,
121.9,120.1,118.9,111.5,91.2,60.2,48.8.Anal.Calcd.for C29H23BrN4:C,68.64;H,4.57;N,11.04;Found:C,68.38;H,4.61;N,11.07%.
实施例3
配体L3的合成
(1)2-溴甲基-8-异丙基喹啉的合成
硼氢化钠(3.61g,95.4mmol)逐批加入8-异丙基喹啉-2-甲醛(9.50g,47.7mmol)的乙醇溶液中,50℃搅拌5h,过滤,旋去乙醇,50mL二氯甲烷溶解,水洗,分液,干燥,过滤,旋去溶剂得橙黄色液体(8-异丙基喹啉-2-甲醇)。冰水浴中,甲磺酰氯(6.49g,56.6mmol)滴加到上一步粗产物、三乙胺(7.16g,70.8mmol)的二氯甲烷溶液中。室温搅拌2h,加100mL水,分液,饱和食盐水洗,干燥,过滤,旋去溶剂得棕色液体(甲磺酸[(8-异丙基喹啉-2-)甲基]酯)。100mL无水丙酮溶解上一步粗产物、溴化锂(20.0g,0.230mol),80℃回流48h,旋干,100mL二氯甲烷溶解,水洗,分液,干燥,过滤,旋转蒸发除去溶剂得棕色液体,柱层析分离(石油醚)得淡黄色液体(7.50g,产率61.7%)。1H NMR(CDCl3,400MHz):δ8.13(d,1H,3J=8.4Hz,),7.62(td,2H,3J=8.0Hz,4J=1.2Hz),7.55(d,1H,3J=8.4Hz),7.51(t,1H,3J=7.6Hz),4.74(s,2H),4.35(m,1H),1.39(d,6H,3J=6.9Hz).
(2)配体L3的合成
除原料采用2-溴甲基-8-异丙基喹啉(3.52g,13.3mmol)、(3-溴-1H-吲哚基-2-)甲胺(1.50g,6.66mmol)外,其余操作步骤同实施例1。浅黄色晶体(1.90g,产率为48.2%)。1H NMR(400MHz,CDCl3):δ11.10(brs,1H),8.16(d,2H,3J=8.4Hz),7.73-7.63(m,7H),7.61(d,1H,3J=7.6Hz),7.53(t,2H,3J=8.0Hz),7.49(d,1H,3J=7.6Hz),7.30(t,1H,3J=7.6Hz),7.23(t,1H, 3J=7.6Hz),4.54(hept,2H,3J=7.0Hz),4.10(s,4H),4.03(s,2H),1.46(d,12H,3J=7.0Hz).13CNMR(100MHz,CDCl3):δ158.3,146.8,145.2,137.1,135.0,132.5,127.5,127.4,126.3,125.4,
125.4,122.6,121.5,120.1,118.9,111.1,91.5,59.9,48.0,27.2,23.7.Anal.Calcd.for C35H35BrN4·0.3C6H14:C,71.59;H,6.40;N,9.07;Found:C,71.73;H,6.29;N,9.12%.
实施例4
配体L4的合成
(1)(±)-1-(1H-吲哚基-2-)乙胺的合成
1)2-乙酰基-1H-吲哚的合成
冰水浴中,1.6M甲基锂的乙醚溶液(41.6mL,66.6mmol)逐滴滴加到(1H-吲哚-2-)甲酸(2.15g,13.3mmol)的200mL无水乙二醇二甲醚溶液中,90℃回流24h,饱和氯化铵水溶液淬灭反应,分液,干燥,过滤,旋干,石油醚重结晶得淡黄色晶体(2.01g,产率94.8%)。 1H NMR(CDCl3,400MHz):δ9.16(s,1H),7.72(d,1H,3J=8.0Hz),7.43(d,1H,3J=8.4Hz),7.35(t,2H,3J=7.6Hz),7.22(d,1H,4J=1.6Hz),7.16(t,2H,3J=7.6Hz),2.61(s,3H).
2)1-(1H-吲哚-2-)甲基酮肟的合成
氢氧化钠的乙醇溶液(14.1g,0.353mol,100mL)滴加到上一步产物和盐酸羟胺(8.70g,0.126mol)的乙醇溶液中,90℃回流4h,过滤,旋转蒸发除去溶剂,100mL水溶解,调节pH值至中性,二氯甲烷萃取,旋干,乙酸乙酯重结晶得白色固体(0.95g,产率43.3%)。1H NMR(CDCl3,400MHz):δ10.35(s,1H),7.68(d,1H,3J=8.0Hz),7.43(d,1H,3J=8.4Hz),7.30(t,1H, 3J=8.0),7.14(t,1H,3J=7.6Hz),6.86(d,1H,4J=1.2Hz),2.37(s,3H),1.69(br,1H).
3)(±)-1-(1H-吲哚基-2-)乙胺的合成
氩气保护下,上一步产物的四氢呋喃溶溶液滴加到氢化铝锂(3.83g,0.101mol)的四氢呋喃溶液中。60℃回流24h,饱和氯化钠水溶液淬灭反应,过滤,旋干,乙酸乙酯重结晶得淡黄色固体(0.9g,产率22.2%)。1H NMR(CDCl3,400MHz):δ8.71(s,1H),7.57(d,1H,3J=8.0Hz),7.34(d,1H,3J=8.0Hz),7.21-7.13(m,1H),7.13-7.01(m,1H),6.32(s,1H),4.32(q,1H,3J=6.4Hz),1.72(s,2H),1.53(d,3H,3J=6.4Hz).Mp:98.0~98.9℃.
(2)配体L4的合成
除原料采用2-溴甲基-8-异丙基喹啉(3.63g,13.7mmol)、(±)-1-(1H-吲哚基-2-)乙胺(1.10g,6.86mmol)外,其余操作步骤同实施例1。白色粉末(0.95g,产率为22.8%)。
1H NMR(400MHz,CDCl3):δ10.34(s,1H),8.06(d,2H,3J=8.4Hz),7.64-7.60(m,5H),7.58(d,2H,3J=8.4Hz),7.50(d,2H,3J=7.6Hz),7.48(d,2H,3J=7.6Hz),7.45(d,2H,3J=8.0Hz),7.19(t,1H,3J=7.6Hz),7.09(t,1H,3J=7.6Hz),6.42(brs,1H),4.56(hept,2H,3J=6.8Hz),4.22(q,1H,3J=6.8Hz),4.12(d,2H,3J=14.0Hz),3.95(d,2H,3J=14.0Hz),1.61(d,3H,3J=6.8Hz),1.49(d,6H,3J=6.8Hz),1.44(d,6H,3J=6.8Hz).13C NMR(100MHz,CDCl3):δ159.0,146.8,145.4,141.2,136.8,135.7,128.8,127.4,126.1,125.3,125.2,121.2,121.0,120.1,119.3,110.7,99.5,56.9,52.2,27.2,23.8,23.5,13.8.Anal.Calcd.for C36H38N4:C,82.09;H,7.27;N,10.64;Found:C,81.79;H,7.24;N,10.52%.
实施例5
配体L5的合成:
(1)(±)-1-(1H-吲哚基-2-)-1-戊胺的合成
1)1-(1H-吲哚-2-)正丁基酮的合成
冰水浴中,2.4M正丁基锂的正己烷溶液(104.0mL,0.251mol)逐滴滴加到(1H-吲哚-2-)甲酸(8.00g,49.7mmol)的300mL无水乙二醇二甲醚,90℃回流24h,饱和氯化铵水溶液淬灭反应,分液,干燥,过滤,旋干得红棕色固体,乙醚重结晶得白色鹅毛状固体(6.10g,产率61.0%)。1H NMR(CDCl3,400MHz):δ9.50(s,1H),7.72(d,1H,3J=8.0Hz),7.46(d,1H,3J=8.0Hz),7.35(t,1H,3J=7.6Hz),7.23(s,1H),7.16(t,1H,J=7.6Hz),2.97(t,1H,3J=7.6Hz),1.86-1.75(m,1H),1.53-1.39(m,1H),0.98(t,1H,3J=7.2Hz).
2)1-(1H-吲哚-2-)正丁基酮肟的合成
氢氧化钠的乙醇溶液(38.9g,0.974mol,100mL)滴加到1-(1H-吲哚-2-)正丁基酮(7.00g,34.8mmol)和盐酸羟胺(24.2g,0.348mol)的乙醇溶液中,90℃回流12h,旋转蒸发除去溶剂,加100mL水溶解,调节pH值至中性,二氯甲烷萃取,干燥,旋干得棕黄色粘稠液体(7.50g,产率>98%,核磁干净,一对顺反异构体,直接用于下一步反应)。1H NMR(CDCl3,400MHz):δ7.57(d,1H,isomer a),7.51(dd,1H,3J=6.0Hz,4J=2.8Hz,isomer b),7.14(d,1H,
3J=7.6Hz,isomer a),7.10-6.99(m,5H,isomer a&b),6.54(s,1H,isomer a),6.53(s,1H,isomer b),2.67-2.63(m,2H,isomer b),2.40-2.36(m,2H,isomer a),1.51-1.39(m,4H,isomer a & b),1.31-1.22(m,2H,isomer b),1.19-1.10(m,2H,isomer a),0.77(t,3H,3J=7.2Hz,isomer b),0.77(t,3H,3J=7.2Hz,isomer a).
3)(±)-1-(-1H-吲哚基-2-)戊胺的合成
氩气保护下,1-(1H-吲哚-2-)正丁基酮肟(7.50g,34.7mmol)的四氢呋喃溶液滴加到氢化铝锂(5.27g,0.139mol)的四氢呋喃悬浊液中,60℃回流24h,饱和氯化钠水溶液淬灭反应,过滤,旋干,石油醚和乙酸乙酯混合溶液重结晶得棕色晶体(1.90g,产率27.1%)。1H NMR(400MHz,CDCl3):δ8.77(s,1H),7.56(d,1H,3J=8.0Hz),7.33(d,1H,3J=8.0Hz),7.16-7.12(m,1H),7.08(t,1H,3J=7.2Hz),4.13(t,1H 3J=6.4Hz),1.95(s,2H),1.89-1.77(m,2H),1.69(dt,2H),1.42-1.26(m,2H),0.90(t,1H,3J=6.8Hz).
(2)配体L5的合成
除原料采用2-溴甲基-8-异丙基喹啉(4.96g,18.8mmol)、(±)-1-(1H-吲哚基-2-)-1-戊胺(1.90g,9.39mmol)外,其余操作步骤同实施例1。黄色泡状固体(1.35g,产率为22.2%)。
1H NMR(400MHz,CDCl3):δ10.43(s,1H),8.16(d,2H,3J=8.4Hz),7.69-7.64(m,7H),7.54-7.50(m,3H),7.25(t,1H,3J=7.4Hz),7.15(t,1H,3J=7.4Hz),6.48(s,1H),4.55(hept,2H,
3J=6.8Hz),4.15(d,2H,3J=13.6Hz),3.82(t,1H,3J=7.2Hz),3.73(d,2H,3J=13.6Hz),2.15-2.06(m,1H),1.95-1.86(m,1H),1.48(d,6H,3J=6.8Hz),1.44(d,6H,3J=6.8Hz),1.38-1.31(m,2H),1.29-1.22(m,2H),0.84(t,3H,3J=7.2Hz).13C NMR(100MHz,CDCl3):δ159.4,147.0,145.3,138.3,137.1,135.7,128.6,127.5,126.4,125.5,125.4,121.4,121.4,120.4,119.4,110.9,100.1,57.4,56.2,31.0,29.4,27.3,23.9,23.8,22.8,14.2.Anal.Calcd.for C39H44N4·0.04CH2Cl2:C,81.95;H,7.76;N,9.79;Found:C,81.72;H,7.80;N,9.43%.
实施例6
锌络合物Zn1的合成:
氩气保护下,于Zn[N(SiMe3)2]2(0.386g,1.00mmol)的15mL甲苯溶液中,逐批加入配体L1(0.507g,1.00mmol),溶液变为桔黄色,搅拌过夜,析出黄色固体粉末,静置沉降,过滤,甲苯洗涤后抽除溶剂,得黄色固体(400mg,产率为54.6%)。1H NMR(400MHz,C6D6):δ8.73(d,2H,4J=2.8Hz),7.44(dd,1H,3J=6.0Hz,4J=2.4Hz),7.28(dd,1H,3J=6.0Hz,4J=2.4Hz),7.23(d,2H,3J=8.0Hz),7.15(m,1H),7.05-6.95(m,7H),6.62(dd,2H,3J=8.2Hz,4J=4.4Hz),4.78(d,2H,2J=12.9Hz),4.58(br,2H),4.16(s,2H),0.58(s,18H).Anal.Calcd.for C35H40BrN5Si2Zn:C,57.41;H,5.51;N,9.56;Found:C,57.10;H,5.59;N,9.32%.
实施例7
锌络合物Zn2的合成
除原料采用Zn[N(SiMe3)2]2(0.386g,1.00mmol)、L2(0.507g,1.00mmol)外,其余操作步骤同实施例6。浅黄色固体(600mg,产率为81.9%)。1H NMR(400MHz,C6D6):δ8.47(d, 2H,3J=8.4Hz),7.83(d,1H,3J=8.4Hz),7.79(d,1H,3J=7.6Hz),7.38(ddd,2H,3J=8.4Hz,3J=7.2Hz,4J=1.6Hz),7.27(d,2H,3J=8.4Hz),7.21(dd,2H,3J=8.0Hz,4J=1.2Hz),7.08(dd,2H,3J=7.2Hz,4J=1.2Hz),6.89-6.83(m,2H),6.48(d,2H,3J=8.4Hz),4.72(d,2H,2J=16.4Hz),4.36(s,2H),4.23(d,2H,2J=16.4Hz),0.36(s,18H).Anal.Calcd.for C35H40BrN5Si2Zn:C,57.41;H,5.51;N,9.56;Found:C,57.91;H,5.50;N,9.50%.
实施例8
锌络合物Zn3的合成
除原料采用Zn[N(SiMe3)2]2(0.386g,1.00mmol)、L3(0.591g,1.00mmol)外,其余操作步骤同实施例6。黄色固体(450mg,产率为55.1%)。1H NMR(400MHz,C6D6):δ8.01(d,1H,3J=8.0Hz),7.99(d,1H,3J=7.6Hz),7.50(d,2H,3J=7.6Hz),7.47-7.42(m,3H),7.31(t,1H,
3J=7.6Hz),7.24-7.18(m,4H),6.72(br,2H),4.70(hept,2H,3J=6.4Hz),4.57(d,2H,2J=15.2Hz),4.31-4.04(m,2H),4.21(d,2H,2J=15.2Hz),1.66(d,6H,3J=6.4Hz),1.29(d,3H,3J=6.0Hz),1.22(br,3H),0.12(s,18H).13C NMR(100MHz,C6D6):δ146.5,145.5,142.9,139.2,131.5,127.5,126.4,126.0,121.7,121.6,120.7,119.0,118.4,116.4,86.1,59.2,51.9,28.5,24.2,6.3.Anal.Calcd.for C41H52BrN5Si2Zn·0.4C7H8:C,61.66;H,6.52;N,8.21;Found:C,61.56;H,6.63;N,8.16%.
实施例9
锌络合物Zn4的合成
除原料采用Zn[N(SiMe3)2]2(0.386g,1.00mmol)、L4(0.527g,1.00mmol)外,其余操作步骤同实施例6。黄色固体(500mg,产率为66.5%)。1H NMR(400MHz,C6D6):δ8.07(d,1H,3J=8.4Hz),8.00(d,1H,3J=7.6Hz),7.57(d,1H,3J=8.0Hz),7.53-7.47(m,4H),7.35(t,1H,
3J=7.2Hz or),7.25-7.21(m,4H),7.08-7.00(m,1H,3J=7.2Hz),6.93(d,1H,3J=8.0Hz),6.59 (s,1H),4.96-4.85(m,1H),4.74-4.67(m,3H),4.56(d,1H,2J=14.8),4.59-4.49(m,1H),4.25-4.11(m,1H),1.76(brs,3H),1.66(d,3H,3J=4.0Hz),1.37(d,3H,3J=6.0Hz),1.24(brs,3H),1.20(brs,3H),0.10(s,18H).13C NMR(100MHz,C6D6):δ147.8,146.4,146.2,145.9,145.7,144.3,133.3,127.4,126.4,126.3,122.0,121.9,120.2,119.7,118.0,116.1,98.8,59.1,53.6,28.6,23.9,23.9,16.3,6.4.Anal.Calcd.for C42H55N5Si2Zn:C,67.13;H,7.38;N,9.32;Found:C,67.12;H,7.37;N,9.39%.
实施例10
锌络合物Zn5的合成
除原料采用Zn[N(SiMe3)2]2(0.386g,1.00mmol)、L5(0.569g,1.00mmol)外,其余操作同实施例6。亮黄色绒球状固体颗粒(400mg,产率为50.4%)。1H NMR(400MHz,C6D6):δ8.01(d,1H,3J=8.0Hz),7.98(d,1H,3J=7.6Hz),7.58(d,1H,3J=8.0Hz),7.52-7.43(m,4H),7.32(t,2H,3J=7.2Hz),7.26(t,1H,3J=7.6Hz),7.19-7.18(m,2H),6.89(d,1H,3J=8.4Hz),6.78(brs,1H),6.73(s,1H),4.85-4.66(m,5H),4.44(d,1H,2J=14.8),4.33(d,1H,2J=16.0),2.15-1.97(m,2H),1.82(brs,3H),1.63(d,3H),1.50(d,3H,3J=4.8Hz),1.39-1.11(m,4H),1.29(d,3H,3J=4.8Hz),0.62(t,3H,3J=7.2Hz),0.14(s,18H).13C NMR(100MHz,C6D6):δ146.2,145.9,145.7,144.4,132.9,129.3,128.6,127.6,127.4,126.3,126.1,122.0,121.6,120.0,119.7,118.0,116.2,100.7,64.0,54.3,32.6,30.5,28.6,28.3,23.9,23.7,23.1,14.1,6.5.Anal.Calcd.for C45H61N5Si2Zn·0.8C6H14:C,69.35;H,8.44;N,8.12;Found:C,69.63;H,8.12;N,8.33%.
实施例11
锌络合物Zn6的合成
氩气保护下,用10mL甲苯稀释浓度为1mol/L ZnEt2(1mL,1mmol)的正己烷溶液, 加入配体L1(0.507g,1.00mmol),析出桔黄色固体,搅拌过夜,静置沉降,过滤,甲苯洗涤后抽除溶剂,得黄色固体(400mg,产率为66.7%)。1H NMR(400MHz,C6D6):δ8.51(d,1H, 3J=4.4Hz),8.50(d,1H,3J=4.4Hz),7.92(d,1H,3J=7.6Hz),7.77(d,1H,3J=8.0Hz),7.34(ddd,1H,3J=8.0Hz,3J=7.2Hz,4J=1.2Hz),7.31(dd,2H,3J=8.0Hz,4J=2.0Hz),7.27(1H,ddd,3J=8.0Hz,3J=6.8Hz,4J=1.6Hz),7.14-7.12(m,2H),7.08(dd,3J=7.2Hz,4J=1.6Hz),6.98(d,1H,3J=7.2Hz),6.96(d,1H,3J=7.2Hz),6.61(d,1H,3J=4.4Hz),6.59(d,1H,3J=4.4Hz),4.39(s,4H),4.02(s,2H),1.64(t,3H,3J=8.0Hz),0.57(q,2H,3J=8.0Hz).Anal.Calcd.For C31H27BrN4Zn:C,61.97;H,4.53;N,9.32.Found:C,61.97;H,4.53;N,9.32%.
实施例12
锌络合物Zn7的合成
氩气保护下,于Zn[N(SiMe3)2]2(0.386g,1.00mmol)的15mL甲苯溶液中,逐批加入配体L5(0.569g,1.00mmol),溶液变为桔黄色,搅拌过夜,于其中逐滴加入叔丁醇的甲苯溶液(0.074g,1.00mmol),室温搅拌过夜,真空泵抽干,加约20mL正己烷溶解重结晶得亮黄色球状固体颗粒(340mg,产率为48.6%)。1H NMR(C6D6,400MHz):δ8.04(d,2H,3J=7.6Hz),7.90(br,1H),7.47(d,2H,3J=7.2Hz),7.44(d,2H,3J=6.4Hz),7.35(t,1H,3J=7.4Hz),7.18-7.10(m,2H),6.97(d,1H,3J=7.6Hz),6.94(d,1H,3J=8.0Hz),6.82(s,1H),6.79(d,1H,3J=8.4Hz),6.62(d,1H,3J=7.6Hz),6.23(d,1H,3J=6.8Hz),4.84(hept,1H,3J=6.8Hz),4.70(hept.1H,3J=6.8Hz),4.53(d,1H,2J=12.4Hz),4.47-4.45(m,1H)4.32(d,1H,2J=12.4Hz),4.12(d,1H,2J=14.4Hz),3.84(d,1H,2J=14.4Hz),2.15-2.08(m,1H),2.07-2.00(m,1H),1.85(d,3H,3J=6.8Hz),1.65(s,9H),1.56(d,3H,3J=6.8Hz),1.48-1.36(m,2H),1.37(d,3H,3J=6.8Hz),1.33-1.23(m,2H),1.28(d,3H,3J=6.8Hz),0.86(t,3H,3J=7.2Hz).Anal.Calcd.for C43H52N4OZn:C,73.12;H,7.42;N,7.93;Found:C,72.81;H,7.54;N,7.93%.
实施例13
镁络合物Mg1的合成
氩气保护下,用约15mL甲苯溶解Mg[N(SiMe3)2]2(0.345g,1.00mmol),逐批加入配体L1(0.597g,1.00mmol),溶液变为淡黄色,逐渐析出黄色固体粉末,搅拌过夜,静置沉降,过滤,甲苯洗涤后抽除溶剂,得黄色固体(413mg,产率为59.8%)。1H NMR(400MHz,C6D6):δ10.01(dd,2H,3J=4.8Hz,4J=2.0Hz),7.93(d,1H,3J=8.2Hz),7.75(d,1H,3J=7.6Hz),7.28(td,1H,3J=7.6Hz,4J=1.6Hz),7.23(dd,2H,3J=8.2Hz,4J=1.6Hz),7.18(t,1H,3J=7.6Hz),7.06-7.00(m,4H),6.94(dd,2H,3J=8.4Hz,3J=6.8Hz),6.81(dd,2H,3J=8.2Hz,3J=4.8Hz),4.05(d,2H,2J=13.4Hz),3.75(s,2H),3.50(d,2H,2J=13.4Hz),0.34(s,18H).Anal.Calcd.for C35H40BrMgN5Si2·(0.7C7H8):C,63.42;H,6.08;N,9.27;Found:C,63.18;H,5.89;N,9.00%.
实施例14
镁络合物Mg2的合成
除原料采用Mg[N(SiMe3)2]2(0.345g,1.00mmol)、L2(0.597g,1.00mmol)外,其余操作步骤同实施例13。黄色固体(500mg,产率为72.3%)。1H NMR(400MHz,C6D6):δ9.59(d,2H,3J=8.6Hz),8.08(d,1H,3J=8.2Hz),7.86(d,1H,3J=7.6Hz),7.59(dp,2H,3J=8.6Hz,4J=4.2Hz),7.20(t,1H,3J=7.6Hz),7.18-7.10(m,5H),7.10(d,2H,3J=4.2Hz),6.10(d,2H,3J=8.8Hz),3.77(s,2H),3.45(d,2H,2J=16.9Hz),3.39(d,2H,2J=16.9Hz),0.21(s,18H).Anal.Calcd.for C35H40BrMgN5Si2:C,60.83;H,5.83;N,10.13;Found:C,60.42;H,5.40;N,9.61%.
实施例15
镁络合物Mg3的合成
除原料采用Mg[N(SiMe3)2]2(0.345g,1.00mmol)、L3(0.592g,1.00mmol)外,其余操作步骤同实施例13。黄色固体(413mg,产率为60.8%)。1H NMR(400MHz,C6D6):δ8.02(d,1H,3J=7.6Hz),7.98(d,1H,3J=8.4Hz),7.50(d,2H,3J=8.0Hz),7.47-7.42(m,3H&),7.32(t,1H,3J=7.4Hz),7.26-7.18(m,4H&),6.75(br,2H),4.61(d,2H,2J=15.6Hz),4.45-4.42(m,2H),4.27(br,2H),4.18(d,2H,2J=14.0Hz),1.69(d,6H,3J=6.0Hz),1.32(d,6H,3J=3.6Hz),0.14(s,18H).13C NMR(100MHz,C6D6):δ145.8,145.5,144.2,139.8,139.5,131.6,127.6,126.5,122.0,120.6,118.9,118.4,116.7,87.0,58.2,52.0,28.7,24.4,6.4;Anal.Calcd.for C35H40BrMgN5Si2:C,63.52;H,6.76;N,9.03;Found:C,62.94;H,6.73;N,8.92%.
实施例16
镁络合物Mg4的合成
除原料采用Mg[N(SiMe3)2]2(0.345g,1.00mmol)、L4(0.526g,1.00mmol)外,其余操作步骤同实施例13。淡黄色固体(300mg,产率为42.2%)。1H NMR(400MHz,C6D6):δ8.02(d,2H,3J=8.4Hz),7.56-7.45(m,5H,3J=7.6Hz),7.36(t,1H,3J=7.4Hz),7.27(t,1H,3J=7.4Hz),7.23-7.19(m,4H),6.87(d,1H,3J=8.0Hz),6.64(s,1H),4.88(d,1H,2J=14.8),4.78(q,1H, 3J=5.2Hz),4.54-4.42(m,3H),4.38(d,1H,2J=14.8),4.10(d,1H,2J=12.0),1.72(s,6H),1.48(d,6H,3J=5.2Hz),1.37(d,3H,3J=5.2Hz),0.14(s,18H).Anal.Calcd.for C42H55MgN5Si2:C,71.01;H,7.80;N,9.86;Found:C,70.74;H,8.11;N,9.43%.
实施例17
镁络合物Mg5的合成
除原料采用Mg[N(SiMe3)2]2(0.345g,1.00mmol)、配体L5(0.569g,1.00mmol)外,其余操作步骤同实施例13。雪花状晶体(450mg,产率为59.8%)。1H NMR(400MHz,C6D6):δ8.00(d,1H,3J=7.6Hz),7.96(d,1H,3J=8.0Hz),7.60(d,1H,3J=8.4Hz),7.51(dd,1H,3J=7.2Hz,4J=1.2Hz),7.47(t,1H,3J=4.4Hz),7.42(ddd,1H,3J=8.0Hz,3J=6.8Hz,4J=1.2Hz),7.40(d,1H,3J=7.6Hz),7.36(d,1H,3J=7.6Hz),7.32(ddd,1H,3J=8.0Hz,3J=7.2Hz,4J=0.8Hz),7.29(t,1H,3J=7.6Hz),7.13-7.11(m,1H),7.03-7.00(m,1H),6.87(d,1H,3J=8.0Hz),6.75(s,1H),6.68(brs,1H),4.86(dd,1H,3J=11.2Hz,3J=4.0Hz,NCH-CH2CH2CH2CH3),4.78(d,1H,2J=16.0),4.73(d,1H,2J=14.8),4.55(hept,1H,3J=6.8Hz),4.46(hept,1H,3J=6.8Hz),4.34(d,1H,2J=16.0),4.17(d,1H,2J=14.8),2.41-2.26(m,2H),1.90(d,3H,3J=2.0Hz),1.58(d,3H,3J=2.0Hz),1.50(d,3H,3J=6.8Hz),1.46-1.32(m,4H),1.33(d,3H,3J=6.8Hz),0.68(t,3H,3J=6.8Hz),0.19(s,18H).13C NMR(100MHz,C6D6):δ146.7,146.0,145.9,145.5,133.0,129.3,128.8,127.4,126.6,126.0,122.3,121.7,119.9,119.4,117.8,116.4,101.8,63.9,53.6,33.3,30.2,29.4,28.2,23.9,23.5,23.1,14.2,6.7.Anal.Calcd.for C45H61MgN5Si2:C,71.83;H,8.17;N,9.31;Found:C,71.50;H,8.03;N,8.85%.
实施例18
钙络合物Ca1的合成
氩气保护下,用约15mL甲苯溶解Ca[N(SiMe3)2]2·2THF(0.785g,1.50mmol),逐批加入配体L1(0.761g,1.50mmol),溶液变为黄色,逐渐析出大量浅色固体粉末,搅拌过夜,静置沉降,过滤,甲苯洗涤后抽除溶剂,得淡黄色固体(695mg,产率为65.5%)。1H NMR(400M,C6D6):δ9.94(dd,2H,3J=4.8Hz,4J=1.6Hz),7.65(d,1H,3J=8.0Hz),7.59(d,1H,3J=8.0Hz),7.19(dd,2H,3J=8.4Hz,4J=1.6Hz),7.00-6.95(m,6H&),6.80(d,1H,3J=4.8Hz),6.78(d,1H, 3J=4.4Hz),4.18(d,2H,2J=12.8Hz),3.67(s,2H),3.38(d,2H,2J=12.8Hz),0.54(s,18H,N[Si(CH3)3]2).Anal.Calcd.for C35H40BrCaN5Si2·1.0C7H8:C,63.13;H,6.06;N,8.76;Found:C, 62.74;H,5.85;N,8.37%.
实施例19
钙络合物Ca2的合成
除原料采用Ca[N(SiMe3)2]2·2THF(0.537g,1.06mmol)、配体L2(0.540g,1.06mmol)外,其余操作步骤同实施例18。淡绿色固体(380mg,产率为50.7%)。1H NMR(C6D6,400M):δ9.29(d,2H,3J=7.6Hz),7.80(br,1H),7.63(d,3J=5.6Hz),7.54(t,2H,3J=7.6Hz),7.22(d,2H, 3J=8.4Hz),7.13-6.97(m,6H),6.39(d,2H,3J=8.4Hz),3.59(s,2H),3.40(d,2H,3J=15.6Hz),3.34(d,2H,3J=15.6Hz),0.48(s,18H).Anal.Calcd.for C35H40BrCaN5Si2·(1.0C7H8):C,63.13;H,6.06;N,8.76;Found:C,62.74;H,5.85;N,8.37%.
实施例20
钙络合物Ca3的合成
氩气保护下,配体L3(0.592g,1.00mmol)逐批加到Ca[N(HSiMe2)2]2·2THF(0.754g,2.00mmol)的甲苯溶液中,室温搅拌1h。抽干,正己烷洗得浅绿色固体。1H NMR(C6D6,400M):δ8.18(d,1H,3J=8.0Hz),8.08(d,1H,3J=8.0Hz),7.52-7.48(m,1H),7.49(d,2H,3J=8.4Hz),7.38-7.34(m,1H),7.30(d,2H,3J=7.2Hz),7.20(dd,2H,3J=8.0Hz,4J=1.2Hz),7.12-7.08(m,2H),6.47(d,2H,3J=8.4Hz),4.23(s,2H),4.07(br,2H),3.92(d,2H,2J=16.4Hz),3.77(d,2H,2J=16.4Hz),3.72(hept,2H,3J=6.8Hz),1.32(d,6H,3J=6.8Hz),0.86(d,6H,3J=6.8Hz),-0.39(d,12H,3J=2.8Hz).13C NMR(C6D6,100MHz):δ157.3,145.3,145.2,144.0,140.0,139.3,129.8,127.9,126.8,126.6,125.8,120.0,119.0,117.6,117.0,116.7,84.5,59.0,54.9,30.3,23.8,21.9,3.9.Anal.Calcd.for C39H48BrCaN5Si2:C,61.39;H,6.34;N,9.18;Found:C,61.16;H,6.15;N,8.95%.
实施例21
钙络合物Ca4的合成
除原料采用Ca[N(SiHMe2)2]2·THF(0.377g,1.00mmol)、L4(0.527g,1.00mmol)外,其余操作步骤同实施例18。白色固体(250mg,36.1%)。1H NMR(C6D6,400M):δ8.29(d,1H,3J=7.6Hz),8.15(d,1H,3J=7.6Hz),7.60(t,1H,3J=7.6Hz),7.52(d,1H,3J=8.4Hz),7.48(d,1H, 3J=8.4Hz),7.42(d,1H,3J=8.0Hz),7.40(d,1H,3J=7.6Hz),7.34(d,1H,3J=7.8Hz),7.24-7.19(m,2H),7.15-7.10(m,2H),6.79(s,1H),6.64(d,1H,3J=7.6Hz),6.52(d,1H,3J=7.6Hz),4.98(q,1H,3J=6.8Hz),4.28(d,1H,2J=14.4Hz),4.21(d,1H,2J=18.4Hz),4.23-4.19(m,1H),4.01(br,2H),3.86(d,1H,2J=18.4Hz),3.64(hept,1H,3J=6.4Hz),3.12(d,1H,2J=14.4Hz),1.67(d,3H,3J=6.8Hz),1.42(d,3H,3J=8.0Hz),1.40(d,3H,3J=6.8Hz),0.84(d,3H,3J=6.4Hz),0.81(d,3H,3J=6.4Hz),-0.43(d,12H,3J=9.2Hz).13C NMR(C6D6,100MHz):δ158.2,157.9,148.9,147.6,146.6,145.8,145.6,145.3,140.0,139.7,133.1,132.0,127.6,127.1,126.2,126.2,121.4,119.7,119.6,119.0,117.0,116.2,,98.757.4,55.5,54.2,31.0,26.2,24.1,21.6,21.4,4.7,4.5.Anal.Calcd.for C40H51CaN5Si2·0.3C7H8:C,69.67;H,7.42;N,9.65;Found:C,69.04;H,7.26;N,8.82%.
实施例22
氩气保护下,于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150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60℃干燥24h。转化率:97%,Mn=3.7×104g/mol,分子量分布PDI=1.58,规整度Pr=0.68。
实施例23
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL叔丁醇甲苯溶液。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:[tBuOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应60分钟,加入石油醚终止反应。其余操作同实施例25。转化率:77%,Mn=3.4×104g/mol,分子量分布PDI=1.22,规整度Pr=0.68。
实施例24
除溶剂换成四氢呋喃以外,其余操作同实施例22。反应150分钟,转化率:77%,Mn=4.8×104g/mol,分子量分布PDI=1.77,规整度Pr=0.63。
实施例25
除溶剂换成四氢呋喃以外,其余操作同实施例23。反应60分钟,转化率:90.2%,Mn=3.1×104g/mol,分子量分布PDI=1.34,Pm=0.69。
实施例26
除催化剂换成Zn2以外,其余操作同实施例22。反应210分钟,转化率:90%,Mn=7.8×104g/mol,分子量分布PDI=1.86,规整度Pr=0.66。
实施例27
除催化剂换成Zn2以外,其余操作同实施例23。反应140分钟,转化率:92%,Mn=3.6×104g/mol,分子量分布PDI=1.37,规整度Pr=0.64。
实施例28
除催化剂换成Zn3以外,其余操作同实施例22。反应110分钟,转化率:90%,Mn=4.3×104g/mol,分子量分布PDI=1.53,规整度Pr=0.67。
实施例29
除催化剂换成Zn3以外,其余操作同实施例23。反应60分钟,转化率:92%,Mn=3.0×104g/mol,分子量分布PDI=1.29,规整度Pr=0.70。
实施例30
除催化剂换成Zn4以外,其余操作同实施例22。反应300分钟,转化率:89%,Mn=5.2×104g/mol,分子量分布PDI=1.61,规整度Pr=0.68。
实施例31
除催化剂换成Zn4以外,其余操作同实施例23。反应150分钟,转化率:89%,Mn=2.4×104g/mol,分子量分布PDI=1.28,规整度Pr=0.71。
实施例32
除催化剂换成Zn5以外,其余操作同实施例22。反应150分钟,转化率:86%,Mn=4.4×104g/mol,分子量分布PDI=1.57,规整度Pr=0.68。
实施例33
除催化剂换成Zn5以外,其余操作同实施例23。反应80分钟,转化率:84%,Mn=3.4×104g/mol,分子量分布PDI=1.11,规整度Pr=0.70。
实施例34
除催化剂换成Zn7以外,其余操作同实施例22。反应80分钟,转化率:88%,Mn=3.5×104g/mol,分子量分布PDI=1.11,规整度Pr=0.67。
实施例35
除催化剂换成Zn7,溶剂换成四氢呋喃以外,其余操作同实施例22。反应80分钟,转化率:92%,Mn=3.9×104g/mol,分子量分布PDI=1.12,规整度Pr=0.71。
实施例36
除催化剂换成Zn7,其余操作同实施例23。反应60分钟,转化率:97%,Mn=1.4×104g/mol,分子量分布PDI=1.44,规整度Pr=0.62。
实施例37
除催化剂换成Mg1,溶剂换成四氢呋喃外,其余操作同实施例22。反应30分钟,转化率:91%,Mn=3.1×104g/mol,分子量分布PDI=1.17,规整度Pr=0.52。
实施例38
除催化剂换成Mg1,溶剂换成四氢呋喃外,其余操作同实施例23。反应15分钟,转化率:96%,Mn=2.7×104g/mol,分子量分布PDI=1.18,Pm=0.48。
实施例39
除催化剂换成Mg2,溶剂换成四氢呋喃外,其余操作同实施例22。反应45分钟,转化率:83%,Mn=2.3×104g/mol,分子量分布PDI=1.16,规整度Pr=0.62。
实施例40
除催化剂换成Mg2,溶剂换成四氢呋喃外,其余操作同实施例23。反应20分钟,转化率:85%,Mn=1.2×104g/mol,分子量分布PDI=1.24,Pm=0.52。
实施例41
除催化剂换成Mg3,溶剂换成四氢呋喃外,其余操作同实施例22。反应5分钟,转化率:92%,Mn=5.0×104g/mol,分子量分布PDI=1.73,规整度Pr=0.67。
实施例42
除催化剂换成Mg3,溶剂换成四氢呋喃外,其余操作同实施例23。反应6分钟,转化率: 87%,Mn=3.1×104g/mol,分子量分布PDI=1.25,Pm=0.61。
实施例43
除催化剂换成Mg3,溶剂换成四氢呋喃外,催化剂单体比例变成[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:400外,其余操作同实施例22。反应5分钟,转化率:87%,Mn=7.2×104g/mol,分子量分布PDI=1.59,规整度Pr=0.67。
实施例44
除催化剂换成Mg3,其余操作同实施例22。反应10分钟,转化率:86%,Mn=3.1×104g/mol,分子量分布PDI=1.59,规整度Pr=0.51。
实施例45
除催化剂换成Mg3,其余操作同实施例23。反应2.5分钟,转化率:99%,Mn=3.2×104g/mol,分子量分布PDI=1.91,Pm=0.46。
实施例46
除催化剂换成Mg4,溶剂换成四氢呋喃外,其余操作同实施例22。反应5分钟,转化率:89%,Mn=2.3×104g/mol,分子量分布PDI=1.77,规整度Pr=0.69。
实施例47
除催化剂换成Mg4,溶剂换成四氢呋喃外,其余操作同实施例23。反应2分钟,转化率:96%,Mn=2.7×104g/mol,分子量分布PDI=1.44,Pm=0.62。
实施例48
除催化剂换成Mg4,其余操作同实施例22。反应20分钟,转化率:82%,Mn=5.8×104g/mol,分子量分布PDI=1.67,规整度Pr=0.51。
实施例49
除催化剂换成Mg4,其余操作同实施例23。反应2分钟,转化率:94%,Mn=4.9×104g/mol,分子量分布PDI=1.51,Pm=0.41。
实施例50
除催化剂换成Mg5,溶剂换成四氢呋喃,其余操作同实施例22。反应3分钟,转化率:90%,Mn=6.7×104g/mol,分子量分布PDI=1.59,规整度Pr=0.69。
实施例51
除催化剂换成Mg5,溶剂换成四氢呋喃,其余操作同实施例23。反应10分钟,真空干
燥24h。转化率:95%,Mn=1.6×104g/mol,分子量分布PDI=1.55,Pm=0.58。
实施例52
除催化剂换成Ca1外,其余操作同实施例22。反应15分钟,转化率:95%,Mn=6.2×104g/mol,分子量分布PDI=1.38,规整度Pr=0.58。
实施例53
除催化剂换成Ca1外,其余操作同实施例23。反应3分钟,转化率:92%,Mn=2.9×104g/mol,分子量分布PDI=1.59,Pm=0.43。
实施例54
除催化剂换成Zn7,单体换成L-丙交酯外,其余操作同实施例22。反应20分钟,转化率:98%,Mn=4.1×104g/mol,分子量分布PDI=1.42。
实施例55
除催化剂换成Zn7,单体换成D-丙交酯外,其余操作同实施例22。反应20分钟,转化率:97%,Mn=3.9×104g/mol,分子量分布PDI=1.46。
实施例56
除催化剂换成Zn2,单体换成ε-己内酯(0.114g,1.0mmol)外,其余操作同实施例22。反应10分钟,转化率:99%,Mn=4.6×104g/mol,分子量分布PDI=1.57。
实施例57
除催化剂换成Zn2,单体换成ε-己内酯(0.114g,1.0mmol)外,其余操作同实施例23。反应3分钟,转化率:99%,Mn=3.1×104g/mol,分子量分布PDI=1.29。
实施例58
除催化剂换成Zn7,单体换成β-丁内酯(0.086g,1.0mmol)外,其余操作同实施例22。反应24小时,转化率:95%,Mn=3.2×104g/mol,分子量分布PDI=1.44。
实施例59
除催化剂换成Zn7,单体换成β-丁内酯(0.086g,1.0mmol)外,其余操作同实施例23。反应12小时,转化率:91%,Mn=1.4×104g/mol,分子量分布PDI=1.27。
实施例60
除催化剂换成Zn5,单体换成α-甲基(三亚甲基碳酸酯)(0.116g,1.0mmol)外,其余操作同实施例23。反应4小时,转化率:91%,Mn=2.9×104g/mol,分子量分布PDI=1.25。
Claims (10)
1.一种喹啉取代胺基吲哚类配体(I)及其金属锌、镁、钙化合物(II),其特征在于,具有以下通式:
式(I)和(II)中:
R1代表氢,卤素;
R2代表氢,C1~C10直链、支链结构的烷基;
A1和A2为具有如式(III)或式(IV)所示结构的基团:
A1和A2同时为结构(III)或结构(IV)所示基团;A1和A2为式(IV)所示基团时,两者可以相同或不同;式(IV)中,R3代表氢,C1~C10直链、支链结构的烷基;
式(II)中:
M代表锌、镁、钙;
X代表C1~C6直链、支链结构的烷基,C1~C6直链或支链结构的烷氧基,二(三甲基硅基)胺基,二(二甲基硅基)胺基;
A1和A2通过其氮原子与金属M中心配位;A1和A2同时或不同时与金属中心配位。
2.根据权利要求1所述的喹啉取代胺基吲哚类配体(I)及其金属锌、镁、钙化合物(II),其特征在于,R1为氢,卤素;R2为氢,C1~C6直链、支链结构的烷基;A1和A2为式(IV)所示基团时,R3为C1~C6直链、支链结构的烷基;X为C1~C4直链、支链结构的烷基,C1~C4直链或支链结构的烷氧基,二(三甲基硅基)胺基,二(二甲基硅基)胺基。
3.根据权利要求1所述的喹啉取代胺基吲哚类配体(I)及其金属锌、镁、钙化合物(II),其特征在于,R1为氢、溴;R2为氢、甲基、正丁基;A1和A2为式(IV)所示基团时,R3为氢、异丙基;X为乙基、叔丁氧基、二(三甲基硅)胺基、二(二甲基硅)胺基。
4.权利要求1~3任一项所述的喹啉取代胺基吲哚类配体(I)及其与金属锌、镁、钙化合物(II)的制备方法,包括如下步骤:
当A1与A2相同时,将式(V)所示取代1H-吲哚-2-烷基胺与式(VI)和式(VII)所示含A1或A2基团的溴甲基化合物发生亲核取代反应,以三乙胺作缚酸剂脱除生成的氢溴酸;反应温度为25~50℃,反应时间为24~72小时,然后从反应产物中收集化合物(I);
当A1与A2不同时,将式(V)所示取代1H-吲哚-2-烷基胺先与式(VI)所示含A1基团的溴甲基化合物发生第一次亲核取代反应,以三乙胺作缚酸剂脱除生成的氢溴酸,反应温度为25~50℃,反应时间为24~72小时;再向反应液中加入式(VII)所示含A2基团的溴甲基化合物发生第二次亲核取代反应,反应温度为25~50℃,反应时间为24~72小时,然后从反应产物中收集化合物(I);
任选的,将式(I)所示喹啉取代胺基吲哚类配体化合物与锌、镁或钙的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12~96小时,然后从反应产物中收集目标喹啉取代胺基吲哚基锌、镁或钙化合物(II);
任选的,将式(I)所示喹啉取代胺基吲哚类配体化合物与锌、镁或钙的金属原料化合物在有机介质中反应,之后再加入C1~C6直链或支链结构的醇继续反应,反应温度为0~100℃,反应时间为12~96小时,然后从反应产物中收集目标喹啉取代胺基吲哚基锌、镁或钙化合物(II);
上述制备方法中式(V)、(VI)、(VII)中取代基R1、R2、A1和A2如权利要求1-3任一项所定义;
金属原料化合物具有通式MX2(THF)n,M=Zn、Mg、Ca;n=0,2;X代表C1~C6直链、支链结构的烷基,二(三甲基硅基)胺基,二(二甲基硅基)胺基;
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。
5.根据权利要求4所述的方法,其特征在于,锌、镁或钙的金属原料化合物为二乙基锌、二正丁基镁、二{二(三甲基硅基)胺基}锌、二{二(三甲基硅基)胺基}镁、二{二(三甲基硅基)胺基}二(四氢呋喃)钙、二{二(二甲基硅基)胺基}二(四氢呋喃)钙;喹啉取代胺基吲哚类配体化合物与金属原料化合物的摩尔比为1:0.5~1.5。
6.权利要求1~3任一项所述的喹啉取代胺基吲哚基锌、镁或钙化合物的应用,其特征在于,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开环聚合。
7.根据权利要求6所述的应用,其特征在于,以权利要求1~3任一项所述的喹啉取代胺基吲哚基锌、镁或钙化合物为催化剂,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。
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任一项所述的喹啉取代胺基吲哚基锌、镁或钙化合物为催化剂,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的摩尔比为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。
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任一项所述的喹啉取代胺基吲哚基锌、镁或钙化合物为催化剂,在醇存在下或不加醇,使ε-己内酯在-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。
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任一项所述的喹啉取代胺基吲哚基锌、镁或钙化合物为催化剂,在醇存在下或不加醇,使α-甲基三亚甲基环碳酸酯在-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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