CN112625054A - 一种吲哚环取代的氨基酚氧基锌络合物及其制备方法和应用 - Google Patents
一种吲哚环取代的氨基酚氧基锌络合物及其制备方法和应用 Download PDFInfo
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- CN112625054A CN112625054A CN202011575743.3A CN202011575743A CN112625054A CN 112625054 A CN112625054 A CN 112625054A CN 202011575743 A CN202011575743 A CN 202011575743A CN 112625054 A CN112625054 A CN 112625054A
- Authority
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- Prior art keywords
- substituted
- indole ring
- zinc
- indolyl
- alkyl
- Prior art date
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- Granted
Links
- 239000011701 zinc Substances 0.000 title claims abstract description 54
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000001041 indolyl group Chemical group 0.000 title abstract description 21
- QCTXENUBAFDBER-UHFFFAOYSA-N [O].NC1=C(C=CC=C1)O Chemical class [O].NC1=C(C=CC=C1)O QCTXENUBAFDBER-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000010668 complexation reaction Methods 0.000 title description 2
- 239000003446 ligand Substances 0.000 claims abstract description 37
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical group C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims abstract description 35
- -1 aminophenol oxygroup zinc complexes Chemical class 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 21
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims abstract description 18
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 9
- 150000002596 lactones Chemical group 0.000 claims abstract 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 44
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 40
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 36
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 23
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 239000003208 petroleum Substances 0.000 claims description 19
- 125000004122 cyclic group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- QNHGHNJBZCMVOX-UHFFFAOYSA-M N[Zn]OC1=CC=CC=C1 Chemical class N[Zn]OC1=CC=CC=C1 QNHGHNJBZCMVOX-UHFFFAOYSA-M 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HCUARRIEZVDMPT-UHFFFAOYSA-N Indole-2-carboxylic acid Chemical compound C1=CC=C2NC(C(=O)O)=CC2=C1 HCUARRIEZVDMPT-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 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 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- QXDLPHJEGZJZFU-UHFFFAOYSA-N C[Si](C)(C)N([Zn])[Si](C)(C)C Chemical compound C[Si](C)(C)N([Zn])[Si](C)(C)C QXDLPHJEGZJZFU-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- QXTIBZLKQPJVII-UHFFFAOYSA-N triethylsilicon Chemical compound CC[Si](CC)CC QXTIBZLKQPJVII-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 26
- 239000007787 solid Substances 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000009826 distribution Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 14
- 229920000747 poly(lactic acid) Polymers 0.000 description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- WIMDKCGAUGHBFY-UHFFFAOYSA-N 2-(bromomethyl)-4-methyl-6-tritylphenol Chemical compound CC1=CC(CBr)=C(O)C(C(C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 WIMDKCGAUGHBFY-UHFFFAOYSA-N 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000004626 polylactic acid Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- VFHUJFBEFDVZPJ-UHFFFAOYSA-N 1h-indole-2-carboxamide Chemical class C1=CC=C2NC(C(=O)N)=CC2=C1 VFHUJFBEFDVZPJ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000012694 Lactone Polymerization Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DHVHFHPLOHDSTL-UHFFFAOYSA-N 2-(bromomethyl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(CBr)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 DHVHFHPLOHDSTL-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- WIKNSILRFMHVAY-UHFFFAOYSA-M O(C1=CC=CC=C1)[Zn] Chemical compound O(C1=CC=CC=C1)[Zn] WIKNSILRFMHVAY-UHFFFAOYSA-M 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- 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)
- Indole Compounds (AREA)
Abstract
本发明公开了一类吲哚环取代的氨基酚氧基锌络合物及其制备方法,以及其在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。本发明的吲哚环取代的氨基酚氧基锌络合物是一种高效的内酯开环聚合催化剂,可用于催化丙交酯等内酯的聚合反应;特别对于外消旋丙交酯开环聚合具有较好的效果。本发明的吲哚环取代的氨基酚氧基锌络合物优点十分明显:原料易得,合成路线简单,产物收率高,具有较好的催化活性及立体可调控性,一般情况下能获得高杂规度、高分子量聚酯材料,加入具有辅助配位作用的有机小分子可具有等规选择性。其结构式如下所示:
Description
技术领域
本发明涉及一类吲哚环取代的氨基酚氧基锌络合物,以及这类络合物在内酯聚合中的应用。
背景技术
高分子聚合物材料发展至今已然充斥于人类生活的方方面面。这些材料主要是难以降解的石油基聚合物材料。石油基聚合物材料的大量使用连带着产生能源危机以及白色污染两大社会经济问题。因此,开发具有可持续特性的聚合物材料来逐步替代这些难以降解的石油基材料,成为当前的研究热点。
聚乳酸(也称聚丙交酯,PLA)原料来源于植物资源,是一种可再生、可降解、生物相容性好的热塑性脂肪族聚酯材料。且因其与某些聚烯烃产品具有相似的物理机械性能,而成为一些高价值领域(如医疗、电子领域等)以及包装等基本应用领域的替代选择品。使用后的聚乳酸产品可以将其二次重熔、回收加工再利用,也可以进行堆肥处理,被自然界降解为对环境无毒无害的二氧化碳和水。与石油基聚烯烃产品相比,在可持续生产与后处理方面具有极大的优越性。
聚乳酸有两种合成工艺,一是乳酸直接进行缩聚反应,但反应过程中产生的水很难去除,故一般很难得到高分子量的聚乳酸;二是用合适的催化剂催化乳酸二聚体-丙交酯开环聚合,该方法更易得到高分子量聚合物,且聚合过程更加可控,这也是如今研究最多的方法。
利用金属络合物催化不同种类的丙交酯单体开环聚合可以获得多种微观链结构的聚丙交酯。聚丙交酯的微观结构决定了其物理性质和机械性能。如,无规聚丙交酯呈无定形态,质脆、无拉伸性、降解速度快;等规聚丙交酯或等规嵌段聚丙交酯为半结晶型材料,具有高熔点、良好的热力学性能和拉伸性。因此开发新型结构的金属络合物催化剂实现不同微观结构聚丙交酯的高活性、高可控性合成成为该领域的主要研究方向。
1999年,Coates小组用β-二亚氨基(BDI)双核锌络合物[(BDI)Zn(OiPr)]2作为催化剂催化外消旋丙交酯聚合,可控性好,获得高杂规度的聚丙交酯,Pr=0.94(J.Am.Chem.Soc.,1999,121,11583-11584)。2010年,我们小组报道了多齿氨基酚氧基锌络合物,对丙交酯聚合显示了超高活性,得到无规聚合物(Macromolecules,2010,43,6535-6537),通过调整爪形配位点碳链长度,获得了等规倾向的聚合物(Dalton trans.,2010,39,7897-7910)。2017年,我们小组报道了恶唑啉取代的氨基酚氧基锌络合物,该类络合物表现出高催化活性和高等规选择性,在-40℃,能催化外消旋丙交酯聚合得到Pm=0.93的聚合物(Macromolecules,2017,50,7911-7919)。
在应用于催化丙交酯聚合的催化剂中,金属锌的络合物因金属中心无毒无害、具有良好的生物相容性、且来源广泛,而络合物本身普遍具有高催化活性和高可控性,因此成为理想的研究对象。目前虽然个别锌络合物对外消旋丙交酯的开环聚合表现出了高等规选择性,但其催化活性比起一般无立体选择性的锌络合物降低很多。所以有关锌络合物催化外消旋丙交酯开环聚合的研究工作有待于进一步开展,以期得到集高活性、高立体选择性为一体的高效催化剂,进一步提高工业化潜力。
发明内容
本发明目的之一在于公开一类吲哚环取代的氨基酚氧基锌络合物。
本发明目的之二在于公开一类吲哚环取代的氨基酚氧基锌络合物的制备方法。
本发明目的之三在于公开一类吲哚环取代的氨基酚氧基锌络合物作为催化剂在内酯聚合中的应用。
本发明的技术构思:
氨基酚类配体具有原料易得、合成方便、结构可调等特点,通过变化取代基可以容易地调节电子效应和位阻效应,因此被广泛应用于各类金属络合物的合成。含有吲哚环的化合物在许多领域有着广泛的应用。吲哚环的N原子不具有与金属中心配位的能力,将吲哚结构引入氨基酚类配体中,配体仍将以二齿形式与金属中心配位,而引入的吲哚基团在不参与配位的情况下能在金属中心周围构造出显著的位阻效应,形成一种不同于以往三齿氨基酚类配体的立体电子效应。基于此,我们设想合成具悬垂吲哚取代的氨基酚类配体,用于构筑一类新型的锌络合物催化剂。通过改变配体骨架上各取代基,来调节金属中心的路易斯酸性以及金属中心的空间位阻,以期实现锌络合物以更高活性、更高立体选择性催化外消旋丙交酯开环聚合,进一步提高工业化潜力。
本发明提供的吲哚环取代的氨基酚类配体(I)及其金属锌络合物(II),其特征在于,具有以下通式:
式(I)、(II)中:
R1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;
R2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;
R3~R4分别代表氢,C1~C20直链、支链或环状结构的烷基,C7~C30单或多芳基取代的烷基,卤素;
A代表氨基NR5R6,其中R5~R6分别为C1~C6直链、支链或环状结构的烷基,三甲基硅基,三乙基硅基,二甲基氢硅基,R5和R6可以相同或不同。
更特征的,式(I)、(II)中,R1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;
R2优选为C1~C8直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基;
R3~R4优选为氢,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,卤素;
A优选为二(三甲基硅)氨基,二(三乙基硅)氨基,二(二甲基氢硅)氨基。
式(I)、(II)中,R1优选为甲基、乙基、异丙基、正丁基、叔丁基、环戊基、环己基、正己基、正辛基、苄基、苯乙基;R2优选为甲基、乙基、异丙基、正丁基、环己基、苄基;R3~R4优选为氢、甲基、叔丁基、枯基、三苯甲基;A优选为二(三甲基硅)氨基。
优选的吲哚环取代的氨基酚类配体,其结构式如下:
优选的氨基酚类配体的金属锌络合物结构为:
本发明的吲哚环取代的氨基酚类配体(I)及其锌络合物(II)制备方法如下所示:
将原料2-吲哚甲酸与二氯亚砜在二氯甲烷中加热回流发生酰氯化反应,之后与相应伯胺R1NH2在三乙胺存在下于二氯甲烷中反应得到2-吲哚甲酰胺类化合物(AN)(Bioorg.Med.Chem.Lett.,2016,26:2685–2690);在N,N-二甲基甲酰胺中经氢化钠拔氢后与卤代烃R2X发生亲核取代反应得到N-取代-2-吲哚甲酰胺(BN)(J.Med.Chem.,2017,60:7067–7083),经氢化锂铝还原生成相应仲胺(N)(J.Org.Chem.,2014,79:10284–10295),之后与2-溴甲基-4,6-二取代苯酚(III)反应,反应温度为25~150℃,反应时间为2~72小时,从反应产物中收集配体化合物(I);
任选的,再将式(I)所示的吲哚环取代的氨基酚类配体化合物与锌金属原料化合物在有机介质中反应,反应温度为0~100℃,反应时间为2~96小时,然后从反应产物中收集含吲哚环的氨基酚氧基锌目标化合物(II);
上述制备方法中取代基R1~R4与满足前述的吲哚环取代的氨基酚类配体(I)及其金属锌络合物(II)的各相应基团一致;卤代烃R2X中,X=Cl、Br或I;
锌金属原料化合物具有通式ZnA2,A与本发明吲哚环取代的氨基酚氧基锌络合物(II)所述的相应基团一致。
锌金属原料化合物优选二{二(三甲基硅)胺基}锌;吲哚环取代的氨基酚类配体化合物(I)与锌金属原料化合物的摩尔比为1:1~1.5;所述的有机介质选自四氢呋喃、乙醚、甲苯、苯、石油醚和正己烷中的一种或两种。
本发明所述吲哚环取代的氨基酚类配体(I)的制备方法中,式(III)所示2-溴甲基-4,6-二取代酚的合成可参考文献方法按以下路线由2,4-取代苯酚与多聚甲醛在33%溴化氢的醋酸溶液反应获得(Inorg.Chem.,2002,41,3656;J.Org.Chem.,1994,59,1939):
本发明所述的吲哚环取代的氨基酚类配体的锌络合物是一种高效的内酯聚合催化剂,可用于L-丙交酯、D-丙交酯、rac-丙交酯、meso-丙交酯、ε-己内酯、β-丁内酯、α-甲基三亚甲基环碳酸酯的聚合反应,聚合方式为溶液聚合和熔融聚合。
以本发明所述的吲哚环取代的氨基酚氧基锌络合物为催化剂,使丙交酯在-40~140℃聚合,优选-20~110℃;聚合时催化剂与单体摩尔比为1:1~10000,优选为1:100~5000。
以本发明所述的吲哚环取代的氨基酚氧基锌络合物为催化剂,在醇存在的条件下,使丙交酯在-40~140℃聚合,优选-20~110℃;聚合时催化剂与醇以及单体摩尔比为1:1~50:1~10000,优选为1:1~50:100~5000;所述的醇为C1~C10直链、支链或环状结构的烷基醇,C7~C20单或多芳基取代的烷基醇。
以本发明所述的吲哚环取代的氨基酚氧基锌络合物为催化剂,在加醇或不加醇的条件下,使ε-己内酯聚合,聚合时催化剂与醇以及单体摩尔比为1:0~50:1~10000,优选为1:0~50:100~5000;所述的醇为C1~C10直链、支链或环状结构的烷基醇,C7~C20单或多芳基取代的烷基醇。
本发明提供的催化剂制备方便、性质稳定,同时具有较高的催化活性及高杂规立体选择性;且可通过加入添加剂如4-(N,N-二甲基)吡啶来调节聚合物链的微观立体结构,因此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
原料及中间体的合成:
(1)2-吲哚甲酰胺(AN)的合成
氩气保护下,向250mL三口瓶中加入150mL干燥CH2Cl2,再加入2-吲哚甲酸(30mmol,4.8g),开始搅拌。随后加入SOCl2(60.0mmol,8.57g),加热回流2h后,用旋转蒸发仪蒸除溶剂及过量的二氯亚砜。加入100mLCH2Cl2将其再次溶解,用旋转蒸发仪再次蒸除溶剂,重复三次后,直接用于下一步反应。
氩气保护下,向250mL三口瓶中,加入三乙胺(36mmol,2.62g)和伯胺(36mmol)与100mL干燥CH2Cl2混合均匀。将上述所得2-吲哚甲酰氯溶于50mL干燥CH2Cl2中,滴加至反应体系中。制备AN1与AN2时,滴加完毕后反应瓶中有大量固体存在,继续搅拌过夜,抽滤得到白色固体,用100mL CH2Cl2洗涤三次,抽干后得到AN1或AN2,产率约80%。制备AN3及AN4时,反应液始终为橙红色透明状,通过柱层析纯化(石油醚:乙酸乙酯=1:1),得到橙红色固体即为产物AN3或AN4,产率约70%。
(2)N-烷基取代-2-吲哚甲酰胺(BN)的合成
氩气保护下,向250mL三口瓶中加入AN(24.6mmol)及60mL干燥N,N-二甲基甲酰胺,冰水浴下加入氢化钠(0.98g,24.6mmol,AR,60%),继续搅拌反应30min。恢复至室温,再加入溴乙烷或碘甲烷(29.5mmol),加热至100℃,反应4h左右,TLC跟踪显示反应完成,所得粗品经柱层析纯化(石油醚:乙酸乙酯=12:1)后得白色固体BN,产率约60%。
(3)N-取代吲哚仲胺(N)的合成
氩气保护下,于100mL三口瓶中加入氢化锂铝(2.25g,59.2mmol)及50mL干燥乙醚,冰水浴冷却后分批加入BN(4.00g,14.8mmol)。加热至30℃反应16h,TLC跟踪显示反应完成。冰水浴下,用微湿的硫酸钠淬灭,加入60mL石油醚,搅拌、过滤,滤液旋干后得到淡黄色或淡绿色油状液体即为各仲胺N,产率为85%左右。
1H NMR of N1(CDCl3,400MHz,298K):δ7.93(d,3J=7.8Hz,1H,Indolyl-H),7.67(d,3J=8.2Hz,1H,Indolyl-H),7.53(t,3J=7.6Hz,1H,Indolyl-H),7.43(t,3J=7.4Hz,1H,Indolyl-H),6.72(s,1H,Indolyl-H),4.61(q,3J=7.2Hz,2H,NCH2CH3),4.31(s,2H,Indolyl-CH2N),2.96-2.85(m,1H,NCH),2.35-2.26(m,2H,CH2 of cyclohexyl),2.15-2.09(m,2H,CH2 of cyclohexyl),1.94-2.3(m,1H,CH2 of cyclohexyl),1.74(t,3J=7.2Hz,3H,NCH2CH3),1.65-1.50(m,5H,CH2 of cyclohexyl,overlapped with the previoussignal).
1H NMR of N2(CDCl3,400MHz,298K)δ7.57(d,3J=7.8Hz,1H,Indolyl-H),7.33(d,3J=8.2Hz,1H,Indolyl-H),7.18(t,3J=7.1Hz,1H,Indolyl-H),7.08(t,3J=7.4Hz,1H,Indolyl-H),6.38(s,1H,Indolyl-H),4.26(q,3J=7.2Hz,2H,NCH2CH3),3.92(s,2H,Indolyl-CH2N),3.25-3.15(m,1H,NCH),1.92-1.81(m,2H,CH2 of cyclopentyl),1.78–1.67(m,2H,CH2 of cyclopentyl),1.63–1.50(m,2H,CH2 of cyclopentyl),1.40(t,3J=7.2Hz,3H,NCH2CH3)1.45-1.36(m,2H,CH2 of cyclopentyl,overlapped with the previoussignal).
1H NMR of N3(CDCl3,400MHz,298K)δ7.58(d,3J=7.8Hz,1H,Indolyl-H),7.33(d,3J=8.1Hz,1H,Indolyl-H),7.19(t,3J=7.6Hz,1H,Indolyl-H),7.09(t,3J=7.0Hz,1H,Indolyl-H),6.38(s,1H,Indolyl-H),4.27(q,3J=7.2Hz,2H,NCH2CH3),3.94(s,2H,Indolyl-CH2N),2.70(t,3J=7.1Hz,2H,NCH2CH2),1.50-1.48(m,2H,CH2 ofnhexyl),1.39(t,3J=7.2Hz,3H,NCH2CH3),1.50-1.48(m,6H,CH2 ofnhexyl,overlapped with the previoussignal),0.91(t,3J=6.8Hz,3H,CH3 ofnhexyl).
1H NMR of N4(CDCl3,400MHz,298K)δ7.59(d,3J=7.8Hz,1H,Indolyl-H),7.34(d,3J=8.1Hz,1H,Indolyl-H),7.20(t,3J=7.6Hz,1H,Indolyl-H),7.10(t,3J=7.3Hz,1H,Indolyl-H),6.39(s,1H,Indolyl-H),4.27(q,3J=7.2Hz,2H,NCH2CH3),3.95(s,2H,Indolyl-CH2N),2.72(t,3J=7.1Hz,2H,NCH2CH2),1.40(t,3J=7.2Hz,3H,NCH2CH3),1.55-1.25(m,6H,CH2 ofnbutyl,overlapped with the previous signal),0.95(t,3J=7.3Hz,3H,CH3 ofnbutyl).
1H NMR of N5(CDCl3,400MHz,298K)δ7.60(d,3J=7.8Hz,1H,Indolyl-H),7.32(d,3J=8.1Hz,1H,Indolyl-H),7.23(t,3J=11.1Hz,1H,Indolyl-H),7.12(t,3J=7.2Hz,1H,Indolyl-H),6.41(s,1H,Indolyl-H),3.95(d,3J=0.9Hz,2H,Indolyl-CH2N),3.77(s,3H,NCH3),2.72(t,3J=10.0Hz,2H,NCH2CH2),1.95(m,2H,),1.59-1.22(m,4H,CH2 ofnbutyl),0.96(t,3J=7.3Hz,3H,CH3 ofnbutyl).
实施例2
配体L1的合成
室温下,将仲胺N1(3.64g,14.2mmol)、碳酸钾(2.35g,17.0mmol)及40mL N,N-二甲基甲酰胺加到100mL单口瓶中,搅拌5min后,分批加入2-溴甲基-4,6-二枯基苯酚(5.99g,14.2mmol)。继续搅拌反应4h,TLC追踪显示反应完毕,加60mL水淬灭,用30mL×3的CH2Cl2萃取,合并有机相,再用60mL×6的饱和食盐水洗涤。有机相用无水硫酸镁干燥,过滤,滤液用旋转蒸发仪蒸除溶剂。用二氯甲烷-石油醚体系重结晶,得到白色固体产物L1(5.85g,41.2%)。
1H NMR(CDCl3,400MHz,298K):δ10.06(br s,1H,OH),7.53(d,3J=7.8Hz,1H,Indolyl-H),7.33-7.11(m,13H,10H of ArH and 3H of Indolyl-H),7.08(t,3J=7.0Hz,1H,Indolyl-H),6.78(d,1H,4J=1.6Hz,ArH),6.24(d,1H,4J=1.6Hz,ArH),3.74(s,2H,ArCH2N),3.72-3.62(m,4H,2H of NCH2CH3 and 2H of Indolyl-CH2N),2.48(pesudo t,1H,3J=11.4Hz,NCH),1.80-1.64(m,16H,12H of C(CH3)2Ph and 4H of cyclohexyl),1.62-1.50(m,2H,CH2 of cyclohexyl),1.39-1.25(m,2H,CH2 of cyclohexyl),1.12-0.96(m,5H,3H of NCH2CH3 and 2H of CH2 of cyclohexyl).13C{1H}NMR(CDCl3,100MHz,298K):δ153.7,151.5,140.1,136.6,135.0,128.0,127.7,126.8,126.2,125.9,125.5,124.9,124.9,121.9,121.3,120.5,119.3,109.5,103.7(all of Ar-C and Indolyl-C),57.6(ArCH2N),53.6(IndolylCH2N),46.6(NCH),42.6(C(CH3)2Ph),42.0(C(CH3)2Ph),37.8(NCH2CH3),31.2(C(CH3)2Ph),29.6(C(CH3)2Ph),27.4(CH2of cyclohexyl),26.2(CH2 ofcyclohexyl),25.8(CH2 of cyclohexyl),15.4(NCH2CH3).Anal.Calcd.for C42H50N2O:C,84.24;H,8.42;N,4.68.Found:C,84.00;H,8.11;N,4.50%.
实施例3
配体L2的合成
除反应物为仲胺N1(2.69g,10.5mmol)、碳酸钾(1.74g,12.60mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(4.65g,10.5mmol)外,其它操作与L1的合成一致,用二氯甲烷-石油醚体系重结晶,得白色固体L2(3.93g,60.5%)。
1H NMR(CDCl3,400MHz,298K):δ10.38(br s,1H,OH),7.53(d,3J=7.7Hz,1H,Indolyl-H),7.25-7.05(m,18H,15H of ArH and 3H of Indolyl-H),6.88(d,1H,4J=1.6Hz,ArH),6.76(d,1H,4J=1.6Hz,ArH),6.22(s,1H,Indolyl-H),3.84-3.77(s,2H,ArCH2N;q,3J=7.0Hz,2H,NCH2CH3),3.68(s,2H,Indolyl-CH2N),2.47(pesudo t,1H,3J=7.0Hz,NCH),2.16(s,3H,ArCH3),1.80-1.65(m,4H,CH2 of cyclohexyl),1.63-1.49(m,2H,CH2 of cyclohexyl),1.37-1.23(m,2H,CH2 of cyclohexyl),1.02-1.15(m,5H,2H ofcyclohexyl and 3H of NCH2CH3).13C{1H}NMR(CDCl3,100MHz,298K):δ154.2,146.2,136.7,135.2,133.6,131.3,130.7,128.7,127.9,127.0,126.6,125.4,122.2,121.2,120.5,119.4,109.5,103.3(all of ArC and Indolyl-C),63.3(Ph3C),57.9(ArCH2N),53.4(IndolylCH2N),45.9(NCH),37.9(NCH2CH3),27.4(CH2 of Cyclohexyl),26.2(CH2 ofcyclohexyl),25.9(CH2 of cyclohexyl),21.0(CH2 of cyclohexyl),15.4(NCH2CH3).Anal.Calcd.for C44H46N2O:C,85.40;H,7.49;N,4.53.Found:C,85.56;H,7.46;N,4.51%.
实施例4
配体L3的合成
除反应物为仲胺N2(3.46g,13.5mmol)、碳酸钾(2.24g,16.2mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(4.65g,10.5mmol)外,其它操作与L1的合成一致,用二氯甲烷-石油醚体系重结晶,得白色固体L3(4.72g,57.8%)。
1H NMR(CDCl3,400MHz,298K):δ10.39(br s,1H,OH),7.55(d,3J=7.7Hz,1H,Indolyl-H),7.25-7.07(m,18H,15H of ArH and 3H of Indolyl-H),6.89(d,4J=1.6Hz,1H,ArH),6.75(d,1H,4J=1.6Hz,ArH),6.25(s,1H,Indolyl-H),3.79(s,2H,ArCH2N),3.75(q,3J=7.1Hz,2H,NCH2CH3),3.65(s,2H,Indolyl-CH2N),3.15-3.03(m,1H,NCH),2.16(s,3H,ArCH3),1.67-1.54(m,4H,CH2 of cyclopentyl),1.53-1.36(m,4H,CH2 ofcyclopentyl),1.12(t,3H,3J=7.1Hz,NCH2CH3).13C{1H}NMR(CDCl3,100MHz,298K):δ154.2,146.2,136.6,134.8,133.8,131.3,130.7,128.5,127.9,127.1,126.7,125.4,122.3,121.2,120.5,119.5,109.5,103.2(all of ArC and Indolyl-C),63.4(Ph3C),61.9(ArCH2N),54.7(IndolylCH2N),47.6(NCH),38.0(NCH2CH3),26.8(CH2 of cyclopentyl),24.3(CH2 of cyclopentyl),21.1(ArCH3),15.4(NCH2CH3).Anal.Calcd.for C43H44N2O:C,85.39;H,7.33;N,4.63.Found:C,85.68;H,7.29;N,4.63%.
实施例5
配体L4的合成
除反应物为仲胺N3(3.25g,12.6mmol)、碳酸钾(1.92g,13.9mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(5.14g,12.6mmol)外,其它操作与L1的合成一致,用二氯甲烷-石油醚体系重结晶,得白色固体L4(4.30g,59.3%)。
1H NMR(CDCl3,400MHz,298K):δ10.09(br s,1H,OH),7.55(d,3J=7.7Hz,1H,Indolyl-H),7.30-7.06(m,18H,15H of ArH and 3H of Indolyl-H),6.91(br s,1H,ArH),6.78(br s,1H,ArH),6.23(s,1H,Indolyl-H),3.85(q,3J=7.0Hz,2H,NCH2CH3),3.73(s,2H,ArCH2N),3.64(s,2H,Indolyl-CH2N),2.33(t,3J=7.5Hz,2H,NCH2CH2),2.18(s,3H,ArCH3),1.43-1.32(m,2H,CH2 of n-hexyl),1.0-1.02(m,9H,6H of n-hexyl and 3H of NCH2CH3),0.86(t,3J=6.8Hz,3H,CH3 of n-hexyl).13C{1H}NMR(CDCl3,100MHz,298K):δ154.0,146.2,136.6,134.6,133.8,131.3,130.9,128.8,127.9,127.1,126.9,125.4,122.3,121.3,120.5,119.5,109.5,103.3(all of ArC and Indolyl-C),63.33(Ph3C),58.2(ArCH2N),53.2(IndolylCH2N),49.7(NCH2CH2),38.1(NCH2CH3),31.8(CH2 of n-hexyl),27.1(CH2 ofn-hexyl),25.6(CH2 of n-hexyl),22.7(CH2 of n-hexyl),21.0(ArCH3),15.4(NCH2CH3),14.1(CH3 of n-hexyl).Anal.Calcd.for C44H48N2O:C,85.12;H,7.79;N,4.51.Found:C,85.39;H,7.79;N,4.47%.
实施例6
配体L5的合成
除反应物为仲胺N4(1.98g,8.60mmol)、碳酸钾(1.43g,10.3mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(3.81g,8.60mmol)外,其它操作与L1的合成一致,用二氯甲烷-石油醚体系重结晶,得白色固体L5(4.30g,59.3%)。
1H NMR(CDCl3,400MHz,298K):δ10.10(s,1H,OH),7.55(d,3J=7.7Hz,1H,Indolyl-H),7.30-7.04(m,18H,15H of ArH and 3H of Indolyl-H),6.91(d,4J=1.6Hz,1H,ArH),6.77(s,1H,4J=1.6Hz,ArH),6.24(s,1H,Indolyl-H),3.86(q,3J=7.1Hz,2H,NCH2CH3),3.72(s,2H,ArCH2N),3.64(s,2H,Indolyl-CH2N),2.38-2.30(m,2H,NCH2CH2),2.17(s,3H,ArCH3),1.40-1.30(m,2H,CH2 of n-butyl),1.19-1.03(m,5H,2H of n-butyl and 3H ofNCH2CH3),0.83(t,3J=7.3Hz,3H,CH3 of n-butyl).13C{1H}NMR(CDCl3,100MHz,298K):δ154.0,146.2,136.6,134.5,133.8,131.3,130.9,128.8,127.9,127.1,126.8,125.4,122.2,121.3,120.5,119.5,109.5,103.3(all of ArC and Indolyl-C),63.3(Ph3C),58.2(ArCH2N),53.1(IndolylCH2N),49.7(NCH2CH2),38.1(NCH2CH3),27.9(CH2 of n-butyl),21.1(ArCH3),20.7(CH2 of n-butyl),15.4(NCH2CH3),14.1(CH3 of n-butyl).Anal.Calcd.for C42H44N2O:C,85.09;H,7.48;N,4.73.Found:C,84.83;H,7.24;N,4.55%.
实施例7
配体L6的合成
除反应物为仲胺N5(1.98g,9.20mmol)、碳酸钾(1.52g,11.0mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(4.08g,9.20mmol)外,其它操作与L1的合成一致,用二氯甲烷-石油醚体系重结晶,得白色固体L6(3.21g,60.2%)。
1H NMR(CDCl3,400MHz,298K):δ10.21(br s,1H,OH),7.55(d,3J=7.8Hz,1H,Indolyl-H),7.25-7.07(m,18H,15H of ArH and 3H of Indolyl-H),6.91(d,4J=1.8Hz,1H,ArH),6.76(d,4J=1.8Hz,1H,ArH),6.29(s,1H,IndolylH),3.70(s,2H,ArCH2N),3.63(s,2H,IndolylCH2N),3.28(s,3H,NCH3),2.32(t,3J=7.9Hz,2H,NCH2CH2),2.17(s,3H,ArCH3),1.41-1.28(m,2H,CH2 of n-butyl),1.14-1.05(m,2H,CH2 of n-butyl),0.83(t,3J=7.2Hz,3H,CH3of n-butyl).13C{1H}NMR(CDCl3,100MHz,298K):δ153.9,146.2,137.9,135.1,133.7,131.3,130.9,128.8,127.4,127.1,126.9,125.4,122.2,121.5,120.4,119.6,109.3,103.5(all of ArC and Indolyl-C),63.3(Ph3C),58.3(ArCH2N),53.1(IndolylCH2N),49.7(NCH2CH2),29.9(NCH3),27.9(CH2 of n-butyl),21.1(ArCH3),20.7(CH2 of n-butyl),14.1(CH3 of n-butyl).Anal.Calcd.for C41H42N2O:C,85.08;H,7.31;N,4.84.Found:C,85.03;H,7.15;N,4.63%.
实施例8
锌络合物Zn1的合成
于50mL的Schlenk瓶中加入Zn[N(SiMe3)2]2(386mg,1.00mmol)及3mL甲苯。称取配体L1(599mg,1.00mmol)溶于5mL甲苯,搅拌下将其滴入前述Schlenk瓶中。搅拌反应12h,过滤,滤液抽干溶剂所得淡黄色泡状固体即为络合物Zn1(807mg,98%)。
1H NMR(C6D6,400MHz,298K):δ7.79-7.74(m,1H,Indolyl-H),7.69(d,4J=2.3Hz,1H,ArH),7.49(d,3J=7.4Hz,2H,ArH),7.35(d,3J=7.2Hz,2H,ArH),7.27-7.10(m,5H ofArH,Indolyl-H and 2H×0.3of toluene),7.08-6.90(m,4H of ArH,Indolyl-H and 3H×0.3toluene),6.43(d,4J=2.3Hz,1H,ArH),6.45-6.39(br s,1H,Indolyl-H,overlappedwith the previous signal),3.79(d,2J=14.9Hz,1H,ArCH2N),3.69(d,2J=12.7Hz,1H,Indolyl-CH2N),3.50(dq,2J=14.9Hz,3J=7.3Hz,1H,NCH2CH3),3.38(d,2J=14.9Hz,1H,ArCH2N),3.13(dq,2J=14.9,3J=6.3Hz,1H,NCH2CH3),3.08(d,2J=12.7Hz,1H,Indolyl-CH2N),2.60(tt,3J=11.4Hz,3J=2.7Hz,1H,NCH),2.10(s,3H×0.3,toluene),2.00(s,3H,ArCH3),1.81(s,3H,ArCH3),1.75(s,3H,ArCH3),1.64(s,3H,ArCH3),1.37-1.58(m,4H,CH2 ofcyclohexyl),1.23-1.10(m,2H,CH2 of cyclohexyl),1.00-0.80(m,4H,CH2 ofcyclohexyl),0.71(t,3J=7.2Hz,3H,NCH2CH3),0.23(s,18H,N(SiMe3)2).13C{1H}NMR(C6D6,100MHz,298K):161.1(NC=CH),153.0(NC),152.1,128.9,128.5,127.2,126.2,125.8,125.6,124.9,122.8,121.8,120.7,110.0,103.9(all of ArC),63.5(ArCH2N),55.8(Indolyl-CH2N),44.9(NCH),42.8(C(CH3)2Ph),42.6(C(CH3)2Ph),37.7(NCH2CH3),31.8(C(CH3)2Ph),31.5(C(CH3)2Ph),31.4(C(CH3)2Ph),30.9(C(CH3)2Ph),29.5(CH2ofcyclohexyl),26.1(CH2 of cyclohexyl),25.7(CH2 of cyclohexyl),15.2(NCH2CH3),5.6(N(SiMe3)2).Anal.Calcd.for C48H67N3OSi2Zn·0.3C7H8:C,70.69;H,8.22;N,4.94.Found:C,70.35;H,8.11;N,4.44%.
实施例9
锌络合物Zn2的合成
于50mL的Schlenk瓶中加入Zn[N(SiMe3)2]2(579mg,1.50mmol)及3mL甲苯。称取配体L2(619mg,1.00mmol)溶于7mL甲苯,搅拌下将其滴入前述Schlenk瓶中。搅拌反应12h,过滤,滤液抽干溶剂后得淡橙色泡状固体。用四氢呋喃将其溶解,浓缩至饱和状态,加入少量正己烷,在室温下放置8h,析出大量晶体,倒出母液,用少量正己烷洗涤,抽干得到白色固体Zn2(362mg,43%)。
1H NMR(C6D6,400MHz,298K):δ7.84-7.74(m,1H,Indolyl-H),7.59(d,3J=7.5Hz,6H,ArH),7.43(d,4J=2.0Hz,1H,ArH),7.30-7.20(m,2H,Indolyl-H),7.19-7.15(m,6H,ArH),7.06-7.01(m,3J=6.8Hz,4H,3H of ArH and 1H of Indolyl-H),6.46(br s,1H,Indolyl-H),6.18(d,4J=2.0Hz,1H,ArH)),3.93-3.80(m,2H,1H of ArCH2N and 1H ofIndolyl-CH2N),3.46(dq,2J=14.6,3J=7.4Hz,1H,NCH2CH3),3.38(d,2J=15.1Hz,1H,ArCH2N),3.19(d,2J=12.0Hz,1H,Indolyl-CH2N),2.99-2.84(m,1H,NCH2CH3),2.64(pesudot,3J=11.2Hz,1H,NCH),2.06(s,3H,ArCH3),1.75-1.67(br s,1H,CH2 of cyclohexyl),1.64(br d,2J=10.0Hz,1H,CH2 of cyclohexyl),1.58-1.48(m,2H,CH2 of cyclohexyl),1.46-1.33(m,2H,CH2 of cyclohexyl),1.20-1.07(m,1H,CH2 of cyclohexyl),0.99-0.80(m,3H,CH2 of cyclohexyl),0.71(t,3J=7.2Hz,3H,NCH2CH3),0.16(s,18H,N(SiMe3)2).13C{1H}NMR(C6D6,100MHz,298K):δ161.2(NC=CH),147.3(NC),137.0,136.7,132.6,131.9,131.2,131.1,127.3,125.4,122.8,122.7,121.5,120.8,120.7,109.9,104.4(all ofArC),64.2(CPh3),64.0(ArCH2N),62.9(Indolyl-CH2N),55.6(NCH),37.4(NCH2CH3),31.1(CH2 of cyclohexyl),25.9(CH2 of cyclohexyl),25.6(CH2 of cyclohexyl),20.9(ArCH3),15.3(NCH2CH3),5.6(N(SiMe3)2).Anal.Calcd.for C50H63N3OSi2Zn:C,71.19;H,7.53;N,4.98.Found:C,70.98;H,7.64;N,4.98%.
实施例10
锌络合物Zn3的合成
于50mL的Schlenk瓶中加入Zn[N(SiMe3)2]2(579mg,1.50mmol)及3mL甲苯。称取配体L3(605mg,1.00mmol)溶于7mL甲苯,搅拌下将其滴入前述Schlenk瓶中。搅拌反应12h,过滤,滤液抽干溶剂后得淡橙色泡状固体。用四氢呋喃溶解,浓缩至饱和状态,加入少量正己烷,在室温下放置12h,析出大量晶体。倒出母液,用少量正己烷洗涤晶体,抽干得到白色固体Zn3(379mg,45.7%)。
1H NMR(C6D6,400MHz,298K):δ7.78-7.74(m,1H,Indolyl-H),7.58(d,3J=7.5Hz,6H,ArH),7.37(d,4J=1.8Hz,1H,ArH),7.30-7.23(m,2H,Indolyl-H),7.19(t,3J=7.5Hz,6H,ArH),7.12(d,3J=8.8Hz,1H,Indolyl-H),7.05(t,3J=7.3Hz,3H,ArH),6.35(s,1H,Indolyl-H),5.87(d,4J=1.8Hz,1H,ArH),3.90(d,2J=15.1Hz,1H,ArCH2N),3.87(d,2J=13.1Hz,1H,Indolyl-CH2N),3.56(t,4H×0.5,THF),3.35(d,2J=15.1Hz,1H,ArCH2N),3.39-3.30(m,1H,NCH2CH3,overlapped with previous signal),3.16-3.08(m,1H,NCH),2.89(d,2J=13.1Hz,1H,Indolyl-CH2N),2.49(dq,2J=15.5Hz,3J=7.5Hz,1H,NCH2CH3),1.98(s,3H,ArCH3),1.83-1.74(m,1H,CH2 of cyclopentyl),1.72-1.50(m,5H,CH2 ofcyclopentyl),1.41(t,4H×0.5,THF),1.34-1.18(m,2H,CH2 of cyclopentyl),0.64(t,3J=7.1Hz,3H,NCH2CH3),0.13(s,18H,N(SiMe3)2).13C{1H}NMR(C6D6,100MHz,298K):δ161.0(NC=CH),147.4(NC),137.4,136.9,132.7,131.9,131.2,130.9,127.3,125.4,122.9,122.9,121.8,120.8,120.2,110.0,104.8(all of ArC),64.3(CPh3),58.7(ArCH2N),57.0(Indolyl-CH2N),47.4(NCH),37.5(NCH2CH3),28.8(CH2 of cyclopentyl),21.0(ArCH3),15.2(CH2 of cyclopentyl),14.0(NCH2CH3),5.5(N(SiMe3)2).Anal.Calcd.forC49H61N3OSi2Zn·0.5C4H8O:C,70.76;H,7.57;N,4.85.Found:C,70.20;H,7.50;N,4.77%.
实施例11
锌络合物Zn4的合成
于50mL的Schlenk瓶中加入Zn[N(SiMe3)2]2(463mg,1.20mmol)及3mL甲苯。称取配体L4(621mg,1.00mmol)溶于7mL甲苯,搅拌下将其滴入前述Schlenk瓶中。搅拌反应12h,过滤,滤液抽干溶剂后得淡橙色泡状固体。用二氯甲烷溶解,浓缩至饱和状态,加入少量正己烷,在室温下放置6h,析出粉末状固体。倒出母液,再用少量正己烷洗涤,抽干得白色固体粉末Zn4(333mg,41.5%)。
1H NMR(C6D6,400MHz,298K):δ7.76(dd,3J=6.8,4J=1.6Hz,1H,Indolyl-H),7.60(d,3J=7.4Hz,6H,ArH),7.46(d,4J=1.9Hz,1H,ArH),7.28-7.20(m,2H,Indolyl-H),7.18(d,3J=6.6Hz,6H,ArH),7.07-7.03(t,3J=7.3Hz,3H of ArH and 1H of Indolyl-H),6.31(d,4J=1.8Hz,1H,ArH),6.26(s,1H,Indolyl-H),4.25(s,2×0.1,CH2Cl2),3.80(d,2J=13.3Hz,1H,ArCH2N),3.75(d,2J=14.8Hz,1H,Indolyl-CH2N),3.47(dq,2J=14.5Hz,3J=7.3Hz,1H,NCH2CH3),3.22(d,2J=14.6Hz,1H,ArCH2N),3.15-2.99(m,2H,1of Indolyl-CH2Nand 1of NCH2CH3),2.63(td,2J=12.2,3J=6.1Hz,1H,NCH2CH2),2.30(td,2J=12.2,3J=4.6Hz,1H,NCH2CH2),2.12(s,3H,ArCH3),1.72(br s,1H,CH2 of n-hexyl),1.39(br s,1H,CH2 of n-hexyl),1.30–1.15(m,4H,CH2 of n-hexyl),1.14–0.95(m,2H,CH2 of n-hexyl),0.88(t,3J=6.9Hz,3H,NCH2CH3),0.72(t,3J=7.1Hz,3H,CH3 of n-hexyl),0.09(s,18H,N(SiMe3)2).13C{1H}NMR(C6D6,100MHz,298K):δ161.0(NC=CH),147.4(NC),137.4,136.9,132.7,131.9,131.2,130.8,127.3,125.4,122.9,122.8,121.8,120.9,120.2,110.0,104.9(all of ArC),64.3(CPh3),58.7(ArCH2N),57.4(Indolyl-CH2N),47.6(NCH2CH2),37.6(NCH2CH3),31.7(CH2 of n-hexyl),27.3(CH2 of n-hexyl),26.8(CH2 of n-hexyl),22.8(CH2 of n-hexyl),21.0(ArCH3),15.2(CH2 of n-hexyl),14.2(CH3 of n-hexyl),5.5(N(SiMe3)2).Anal.Calcd.for C50H65N3OSi2Zn·0.1CH2Cl2:C,70.45;H,7.69;N,4.92.Found:C,70.03;H,7.59;N,4.88%.
实施例12
锌络合物Zn5的合成
于50mL的Schlenk瓶中加入Zn[N(SiMe3)2]2(463mg,1.20mmol)及3mL甲苯。称取配体L5(593mg,1.00mmol)溶于7mL甲苯,搅拌下将其滴入前述Schlenk瓶中。搅拌反应12h,过滤,滤液抽干溶剂后得淡绿色泡状固体。用四氢呋喃溶解,浓缩至饱和状态,加入少量正己烷,在室温下放置6h,析出粉末状固体。倒出母液,再用少量正己烷洗涤,抽干得白色固体粉末Zn5(379mg,40.6%)。
1H NMR(C6D6,400MHz,298K):δ7.76(dd,3J=6.7Hz,4J=1.7Hz,1H,Indolyl-H),7.59(d,3J=7.4Hz,6H,ArH),7.46(d,4J=1.9Hz,1H,ArH),7.27-7.21(m,2H,Indolyl-H),7.18(d,3J=7.4Hz,6H,ArH),7.09–7.01(m,4H,3H of ArH and 1H of Indolyl-H),6.29(d,4J=1.9Hz,1H,ArH),6.23(s,1H,Indolyl-H),3.77(d,2J=14.7Hz,1H,ArCH2N),3.72(d,2J=14.9Hz,1H,Indolyl-CH2N),3.56(t,4H×0.2,THF),3.52-3.39(m,1H,NCH2CH3),3.20(d,2J=13.4Hz,1H,ArCH2N),3.1-2.9(m,2H,1H of Indolyl-CH2N and 1H of NCH2CH3),2.61(td,2J=12.3Hz,3J=3.9Hz,1H,NCH2CH2),2.26(td,2J=12.3Hz,3J=4.7Hz,1H,NCH2CH2),2.11(s,3H,ArCH3),1.67(br s,1H,CH2 of n-butyl),1.40(t,4H×0.2,THF),1.35(br s,1H,CH2 of n-butyl),1.09–0.94(m,2H,CH2 of n-butyl),0.80(t,3J=7.3Hz,3H,NCH2CH3),0.71(t,3J=7.0Hz,3H,CH3 of n-butyl),0.09(s,18H,N(SiMe3)2).13C{1H}NMR(C6D6,100MHz,298K):δ161.2(NC=CH),147.4(NC),136.9,136.5,132.6,131.9,131.4,128.9,127.3,125.4,122.7,122.7,121.0,120.7,119.9,109.9,104.0(all of ArC),67.8(THF),66.5(CPh3),64.2(ArCH2N),57.9(Indolyl-CH2N),45.2(NCH2CH2),36.9(NCH2CH3),32.0(CH2 of n-butyl),31.3(NCH2CH3),25.8(THF),23.7(CH2 of n-butyl),20.8(ArCH3),15.5N(CH3 of n-butyl),5.5(N(SiMe3)2).Anal.Calcd.for C48H61N3OSi2Zn·0.2C4H8O:C,70.45;H,7.58;N,5.05.Found:C,70.05;H,7.47;N,4.32%.
实施例13
锌络合物Zn6的合成
于50mL的Schlenk瓶中加入Zn[N(SiMe3)2]2(463mg,1.20mmol)及3mL甲苯。称取配体L6(579mg,1.00mmol)溶于7mL甲苯,搅拌下将其滴入前述Schlenk瓶中。搅拌反应12h,过滤,滤液抽干溶剂后得白色固体。用四氢呋喃溶解,浓缩至饱和状态,加入少量正己烷,在室温下放置6h,析出粉末状固体。倒出母液,再用少量正己烷洗涤,抽干得白色固体粉末Zn6(333mg,41.5%)。
1H NMR(C6D6,400MHz,298K):δ7.75(d,3J=7.2Hz,1H,Indolyl-H),7.59(d,3J=7.5Hz,6H,ArH),7.45(d,4J=2.0Hz,1H,ArH),7.30-7.20(m,2H,IndolylH),7.17(d,3J=7.5Hz,6H,ArH),7.05–7.01(m,4H,3H of ArH and 1H of Indolyl-H),6.27(d,4J=1.8Hz,1H,ArH),6.21(s,1H,Indolyl-H),3.72(d,2J=12.5Hz,1H,ArCH2N),3.56(d,2J=12.0Hz,1H,Indolyl-CH2N),3.08-2.90(m,2H,1H of ArCH2N and 1H of Indolyl-CH2N),2.54(s,3H,NCH3),2.61-2.50(m,1H,NCH2CH2,overlapped with previous signal),2.28-2.14(m,1H,NCH2CH2),2.11(s,3H,ArCH3),1.63(br s,1H,CH2 of n-butyl),1.29(br s,1H,CH2 ofn-butyl),1.10-0.90(m,2H,CH2 of n-butyl),0.79(t,3J=7.3Hz,3H,CH3 of n-butyl),0.09(s,18H,N(SiMe3)2).13C{1H}NMR(C6D6,100MHz,298K):160.9(NC=CH),147.4(NC),138.1,137.5,132.7,131.9,131.6,131.1,127.3,125.4,122.9,122.7,121.5,120.8,120.2,109.9,104.6(all of ArC),65.8(CPh3),64.3(ArCH2N),58.7(Indolyl-CH2N),47.7(NCH2CH2),29.2(NCH3),28.6(CH2 of n-butyl),21.0(CH2 of n-butyl),20.9(ArCH3),13.9(CH3 of n-butyl),5.52(N(SiMe3)2).Anal.Calcd.for C47H59N3OSi2Zn:C,70.25;H,7.40;N,5.23.Found:C,70.03;H,7.52;N,5.12%.
实施例14
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的THF溶解。量取催化剂Zn1的THF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±1℃,反应90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:85%,Mn=2.85×104g/mol,分子量分布PDI=1.42,杂规度Pr=0.83。
实施例15
除催化剂换成Zn2外,其他操作同实施例14,反应160min后,转化率:92%,Mn=3.97×104g/mol,分子量分布PDI=1.54,杂规度Pr=0.89。
实施例16
除催化剂换成Zn3外,其他操作同实施例14,反应120min后,转化率:86%,Mn=4.14×104g/mol,分子量分布PDI=1.49,杂规度Pr=0.90。
实施例17
除催化剂换成Zn4外,其他操作同实施例14,反应180min后,转化率:87%,Mn=4.22×104g/mol,分子量分布PDI=1.53,杂规度Pr=0.95。
实施例18
除催化剂换成Zn5外,其他操作同实施例14,反应160min后,转化率:87%,Mn=6.65×104g/mol,分子量分布PDI=1.53,杂规度Pr=0.95。
实施例19
除催化剂换成Zn6外,其他操作同实施例14,反应150min后,转化率:91%,Mn=4.11×104g/mol,分子量分布PDI=1.45,杂规度Pr=0.88。
实施例20
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL异丙醇的THF溶液溶解。量取催化剂Zn4的THF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±1℃,反应35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:90%,Mn=2.52×104g/mol,分子量分布PDI=1.33,杂规度Pr=0.83。
实施例21
除催化剂换成Zn6外,其他操作同实施例20,反应40min后,转化率:88%,Mn=2.54×104g/mol,分子量分布PDI=1.32,杂规度Pr=0.83。
实施例22
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),加入0.5mL的甲苯溶液。量取催化剂Zn1及4-(N,N-二甲基)吡啶的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[DMAP]0=0.005M,[Zn]0:[DMAP]0:[rac-LA]0=1:1:200。控制反应温度25±1℃,反应60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=3.98×104g/mol,分子量分布PDI=1.58,等规度Pm=0.56。
实施例23
除催化剂换成Zn4外,其他操作同实施例22,反应240min后,转化率:86%,Mn=4.67×104g/mol,分子量分布PDI=1.59,等规度Pm=0.64。
实施例24
除催化剂换成Zn5外,其他操作同实施例22,反应170min后,转化率:86%,Mn=10.3×104g/mol,分子量分布PDI=1.57,等规度Pm=0.60。
实施例25
除催化剂换成Zn6外,其他操作同实施例22,反应60min后,转化率:86%,Mn=4.96×104g/mol,分子量分布PDI=1.56,等规度Pm=0.60。
实施例26
除催化剂换成Zn1外,聚合溶剂换成THF,其他操作同实施例22,反应40min后,转化率:95%,Mn=4.82×104g/mol,分子量分布PDI=1.45,等规度Pm=0.56。
实施例27
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL异丙醇的甲苯溶液溶解。量取催化剂Zn1及DMAP的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[DMAP]0=0.005M,[Zn]0:[DMAP]0:[iPrOH]0:[rac-LA]0=1:1:1:200。控制反应温度25±1℃,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:95%,Mn=2.46×104g/mol,分子量分布PDI=1.24,等规度Pm=0.53。
实施例28
除催化剂换成Zn4外,其他操作同实施例27,反应30min后,转化率:88%,Mn=2.19×104g/mol,分子量分布PDI=1.31,等规度Pm=0.63。
实施例29
除催化剂换成Zn3外,聚合溶剂换成THF,单体换成L-丙交酯,其他操作同实施例27,反应10min后,转化率:90%,Mn=2.42×104g/mol,分子量分布PDI=1.25。
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),加入0.5mL的甲苯溶液。量取催化剂Zn6及4-(N,N-二甲基)吡啶的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[DMAP]0=0.01M,[Zn]0:[DMAP]0:[rac-LA]0=1:2:200。控制反应温度25±1℃,反应45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:86%,Mn=3.49×104g/mol,分子量分布PDI=1.46,等规度Pm=0.58。
Claims (10)
2.根据权利要求1所述的吲哚环取代的氨基酚类配体(I)及其金属锌络合物(II),其特征在于,R1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;R2为C1~C8直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基;R3~R4为氢,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,卤素;A为二(三甲基硅)氨基,二(三乙基硅)氨基,二(二甲基氢硅)氨基。
3.根据权利要求1所述的吲哚环取代的氨基酚类配体(I)及其金属锌络合物(II),其特征在于,R1为甲基、乙基、异丙基、正丁基、叔丁基、环戊基、环己基、正己基、正辛基、苄基、苯乙基;R2为甲基、乙基、异丙基、正丁基、环己基、苄基;R3~R4为氢、甲基、叔丁基、枯基、三苯甲基;A为二(三甲基硅)氨基。
4.权利要求1~3任一项所述的吲哚环取代的氨基酚类配体(I)及其金属锌络合物(II)的制备方法,包括如下步骤:
将原料2-吲哚甲酸与二氯亚砜在二氯甲烷中加热回流发生酰氯化反应,之后与相应伯胺R1NH2在三乙胺存在下于二氯甲烷中反应得到2-吲哚甲酰胺类化合物(AN);然后在N,N-二甲基甲酰胺中经氢化钠拔氢后与卤代烃R2X发生亲核取代反应得到N-取代-2-吲哚甲酰胺(BN),经氢化锂铝还原生成相应仲胺(N),之后与2-溴甲基-4,6-二取代苯酚(III)反应,反应温度为25~150℃,反应时间为2~72小时,从反应产物中收集配体化合物(I);
任选的,将式(I)所示的吲哚环取代的氨基酚类配体化合物与锌金属原料化合物在有机介质中反应,反应温度为0~100℃,反应时间为2~96小时,然后从反应产物中收集吲哚环取代的氨基酚氧基锌目标化合物(II);
上述制备方法中取代基R1~R4与满足权利要求1~3任一项所述的吲哚环取代的氨基酚类配体(I)及其金属锌络合物(II)的各相应基团一致;卤代烃R2X中,X=Cl、Br或I;
锌金属原料化合物具有通式ZnA2,A与满足权利要求1~3任一项所述的吲哚环取代的氨基酚氧基锌络合物(II)的相应基团一致。
5.根据权利要求4所述的方法,其特征在于,锌金属原料化合物为二{二(三甲基硅)氨基}锌,吲哚环取代的氨基酚类配体化合物与锌金属原料化合物的摩尔比为1:1~1.5;所述的有机介质选自四氢呋喃、乙醚、甲苯、苯、石油醚和正己烷中的一种或两种。
6.权利要求1~3任一项所述的吲哚环取代的氨基酚氧基锌络合物的应用,其特征在于,用于内酯的开环聚合。
7.根据权利要求6所述的应用,其特征在于,内酯选自L-丙交酯,D-丙交酯,rac-丙交酯,meso-丙交酯,ε-己内酯,β-丁内酯,α-甲基三亚甲基环碳酸酯。
8.根据权利要求6所述的应用,其特征在于,以权利要求1~3任一项所述的吲哚环取代的氨基酚氧基锌络合物为催化剂,使丙交酯聚合,聚合时催化剂与单体的摩尔比为1:1~10000。
9.根据权利要求6所述的应用,其特征在于,以权利要求1~3任一项所述的吲哚环取代的氨基酚氧基锌络合物为催化剂,在醇存在的条件下,使丙交酯聚合,聚合时催化剂与醇以及单体摩尔比为1:1~50:1~10000;所述的醇为C1~C10直链、支链或环状结构的烷基醇,C7~C20单或多芳基取代的烷基醇。
10.根据权利要求6所述的应用,其特征在于,以权利要求1~3任一项所述的吲哚环取代的氨基酚氧基锌络合物为催化剂,在加醇或不加醇的条件下,使ε-己内酯聚合;所述的醇为C1~C10直链、支链或环状结构的烷基醇,C7~C20单或多芳基取代的烷基醇。
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CN113307820B (zh) * | 2021-05-13 | 2022-10-25 | 华东理工大学 | 一种喹啉环取代的氨基酚氧基锌络合物及其制备方法和应用 |
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