CN113264901A - 一种含2-取代噻唑-4-基的氨基酚氧基锌络合物及其制备方法和应用 - Google Patents
一种含2-取代噻唑-4-基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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- CN113264901A CN113264901A CN202110525614.1A CN202110525614A CN113264901A CN 113264901 A CN113264901 A CN 113264901A CN 202110525614 A CN202110525614 A CN 202110525614A CN 113264901 A CN113264901 A CN 113264901A
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- Prior art keywords
- substituted
- alkyl
- zinc
- cyclohexyl
- arch
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- 239000011701 zinc Substances 0.000 title claims abstract description 65
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 title abstract description 4
- 239000003446 ligand Substances 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 10
- 150000002596 lactones Chemical class 0.000 claims abstract 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 195
- 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 95
- -1 2-substituted thiazol-4-yl groups Chemical group 0.000 claims description 64
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 125000004122 cyclic group Chemical group 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- QNHGHNJBZCMVOX-UHFFFAOYSA-M N[Zn]OC1=CC=CC=C1 Chemical compound N[Zn]OC1=CC=CC=C1 QNHGHNJBZCMVOX-UHFFFAOYSA-M 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 3
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 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
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- QXTIBZLKQPJVII-UHFFFAOYSA-N triethylsilicon Chemical compound CC[Si](CC)CC QXTIBZLKQPJVII-UHFFFAOYSA-N 0.000 claims description 2
- 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
- DBMWNANFZQEHDV-UHFFFAOYSA-N 1-aminocyclohexa-2,4-dien-1-ol Chemical compound NC1(O)CC=CC=C1 DBMWNANFZQEHDV-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 41
- 230000015572 biosynthetic process Effects 0.000 abstract description 24
- 238000001914 filtration Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- QCTXENUBAFDBER-UHFFFAOYSA-N [O].NC1=C(C=CC=C1)O Chemical compound [O].NC1=C(C=CC=C1)O QCTXENUBAFDBER-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 47
- 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 40
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 34
- 239000007787 solid Substances 0.000 description 28
- 238000009826 distribution Methods 0.000 description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 18
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 description 17
- 239000007858 starting material Substances 0.000 description 15
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 229920000747 poly(lactic acid) Polymers 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000012300 argon atmosphere Substances 0.000 description 10
- 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 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000004626 polylactic acid Substances 0.000 description 6
- 239000012047 saturated solution Substances 0.000 description 6
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical group C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 5
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 5
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 229920000118 poly(D-lactic acid) Chemical group 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000012694 Lactone Polymerization Methods 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- SUNMBRGCANLOEG-UHFFFAOYSA-N 1,3-dichloroacetone Chemical class ClCC(=O)CCl SUNMBRGCANLOEG-UHFFFAOYSA-N 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- OBQYFPBESLPHHK-UHFFFAOYSA-N 2-benzyl-4-(chloromethyl)-1,3-thiazole Chemical compound ClCC1=CSC(CC=2C=CC=CC=2)=N1 OBQYFPBESLPHHK-UHFFFAOYSA-N 0.000 description 2
- GQFSKUWJLINAJD-UHFFFAOYSA-N 2-tert-butyl-4-(chloromethyl)-1,3-thiazole Chemical compound CC(C)(C)C1=NC(CCl)=CS1 GQFSKUWJLINAJD-UHFFFAOYSA-N 0.000 description 2
- QKWSLYINUYKIRF-UHFFFAOYSA-N 4-(chloromethyl)-1,3-thiazole Chemical compound ClCC1=CSC=N1 QKWSLYINUYKIRF-UHFFFAOYSA-N 0.000 description 2
- SVEGSFSFMLCNFF-UHFFFAOYSA-N 4-(chloromethyl)-2-phenyl-1,3-thiazole Chemical compound ClCC1=CSC(C=2C=CC=CC=2)=N1 SVEGSFSFMLCNFF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HKVYINROOPCUIP-UHFFFAOYSA-N 2-chloro-4-(chloromethyl)-1,3-thiazole Chemical compound ClCC1=CSC(Cl)=N1 HKVYINROOPCUIP-UHFFFAOYSA-N 0.000 description 1
- 239000011165 3D composite Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YBDKTAWNNZGBSQ-UHFFFAOYSA-M NCC[Zn]OC1=CC=CC=C1 Chemical compound NCC[Zn]OC1=CC=CC=C1 YBDKTAWNNZGBSQ-UHFFFAOYSA-M 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920000576 tactic polymer Polymers 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D277/28—Radicals substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
本发明公开了一类含2‑取代噻唑‑4‑基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。本发明含2‑取代噻唑‑4‑基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聚合具有好的催化效果。本发明含2‑取代噻唑‑4‑基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,具有很高的催化活性和立体选择性,能获得高规整度、高分子量聚酯材料,能够满足工业部门的需要。其结构式如下所示:
Description
技术领域
本发明涉及一类含2-取代噻唑-4-基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
高分子材料由于其优越的物理和机械性能以及价格低廉、安全可靠等优点而广泛应用在生产生活的方方面面。然而高分子材料中应用最多的聚烯烃材料不能生物降解,造成了严重的污染问题。此外,聚烯烃材料的大量使用加快了不可再生石油资源的消耗。聚丙交酯(也称作聚乳酸)作为生物降解型高分子材料,其原料可再生,材料本身具有比较优秀的物理、机械以及加工性能,被认为最具有潜力在一次性用品、包装行业、纤维工业和医药卫生等领域取代石油基聚合物。
配位开环聚合是当前合成聚丙交酯的最有效的方法,由于聚合过程中不涉及水的生成和除去,使用特定催化剂可以获得具有可控分子量、窄分子量分布和可调立构规整度的聚丙交酯。研究表明,聚丙交酯的立构规整度会极大地影响其化学和物理性质,例如其熔点、结晶度和机械性能等。同时,具有不同链结构及分子量的聚丙交酯,其应用领域也有所不同。改变聚合物链结构序列可以有效调节高分子材料性质,特别是对控制聚合物结晶度和生物降解性是一种非常有效的策略。此外,具有相反构型的有规立构聚合物链之间可以产生立体复合作用,其所形成的互锁结构可以显著改变材料的物理性质。例如,当PLLA和PDLA链以等量均匀混合时,可以形成立体复合物PLA,在立体复合结构中,聚L-LA和聚D-LA序列之间强相互作用,可以增强PLA材料的耐热性、机械性能以及降解性能。在过去几年中,许多的研究已经证明了对映体纯半结晶均聚物(L-乳酸)(PLLA)和聚(D-乳酸)(PDLA)形成的立体复合物具有非常高的熔点,比均聚的PLLA或PDLA的熔点高约50℃。立体复合PLA具有可以与聚苯乙烯塑料媲美的机械能,有望在一定领域取代聚苯乙烯材料。
2002年,Chisholm课题组用β-二亚胺锌络合物催化外消旋丙交酯聚合,得到了较高杂规度的聚乳酸,Pr=0.90(Inorg.Chem.2002,41,2785-2794)。Hillmyer和Tolman课题组在2003年合成了双乙氧基桥联的双核锌络合物,对外消旋丙交酯开环聚合具有很高的催化剂活性,但没有立体选择性(J.Am.Chem.Soc.2003,125,11350)。2010年,我们报道了多齿氨基酚氧基锌络合物,对丙交酯聚合显示了高催化活性,获得了偏等规的聚合物(Daltontrans.,2010,39,7897-7910)。2013年,我们又报道了含有悬垂四氢吡咯的手性氨基酚类系列锌络合物,第一次实现了锌络合物催化外消旋丙交酯较高等规选择性聚合,在-38℃聚合时等规度可达到Pm=0.84(Chem.Common.,2013,49:8686-8688)。2014年,Du课题组合成一系列邻位取代恶唑衍生的类β-二亚胺锌络合物,这类络合物催化rac-LA聚合得到了多嵌段等规聚丙交酯(Pm=0.77-0.91),最高等规选择性Pm=0.91,但催化活性很低(ACS MacroLett.2014,3,689)。2016年,Kol课题组用一系列四齿线型胺基酚氧基乙基锌络合物催化rac-LA聚合,有较好的等规选择性,室温下可达Pm=0.81(Chem.Eur.J.,2016,22:11533-11536)。2016年,Williams课题组组设计合成的系列大环双核锌络合物,对催化外消旋丙交酯具有非常高的活性,TOF=60000h-1,但均没有立体选择性(Angew.Chem.Int.Ed.2016,128,1-7)。2017和2018年,我们分别报道了一系列手性恶唑啉和非手性苯并恶唑取代的氨基酚氧基锌络合物,在催化外消旋丙交酯聚合时同时具有较高活性和较高等规选择性,室温下所得聚合物的Pm=0.89(Macromolecules,2017,50(20),7911-7919;Inorg.Chem.,2018,57(17),11240-11251)。2019年,Chen课题组合成了苯氧基亚胺配体的锌络合物,对外消旋丙交酯聚合表现出良好的立体化学控制,其在室温和低温(-30℃)下均可得到高度杂规的PLA(Pr=0.90,Pr=0.94),分子量分布较窄(Organometallics,2019,38,461-468)。2019年,我们课题组又报道了一类咪唑环取代的氨基酚氧基锌络合物,在催化外消旋丙交酯聚合时能表现出较高活性和高等规选择性,Pm=0.89(Chem.Commun.,2019,55,10112-10115)。
当前研究者在催化外消旋丙交酯开环聚合研究上取得了较多进步,但设计出具有高活性、高立体选择性且合成方法简便的催化剂仍是巨大挑战。虽然目前有一些锌催化剂可以实现外消旋丙交酯高活性、等规选择性开环聚合,但是其性能仍不理想。因此,对丙交酯开环聚合具有高活性、高等规选择性,对杂质等良好耐受性的催化剂的研究开发仍有待进一步深入。
发明内容
本发明目的之一在于公开一类含2-取代噻唑-4-基的氨基酚氧基锌络合物。
本发明目的之二在于公开一类含2-取代噻唑-4-基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含2-取代噻唑-4-基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:
研究表明实现外消旋丙交酯高活性、高等规选择性开环聚合的关键是催化剂,而催化剂的性能由其金属中心的性质以及配体的电子效应和空间效应决定。噻唑是五元杂环,电子云密度大,对金属中心的给电子能力较强,与金属配位后,能较好地稳定金属中心;且其上取代基易于调整,如便于在噻唑2-位引入各类取代基,从而可以方便地实现对其配位能力进行调节。将2-取代噻唑环引入配体结构中,通过对噻唑环2-位取代基的优化调整可以容易地实现对络合物催化剂电子效应和空间效应的调控。同时含有氨基酚类配体具有廉价易得、合成方便、结构易调等优点,因此本发明将噻唑环引入到氨基酚氧基结构中有望获得对外消旋丙交酯开环聚合具有良好的催化活性和选择性的催化剂,进而提升其工业应用价值。
本发明提供的含2-取代噻唑-4-基的氨基酚类配体(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~R2分别代表氢,C1~C20直链、支链或环状结构的烷基,C7~C30的单或多芳基取代烷基,卤素;
R3代表C1~C20直链、支链或环状结构的烷基,C7~C30的单或多芳基取代烷基;
R4分别代表氢,C1~C20直链、支链或环状结构的烷基,C7~C30的单或多芳基取代烷基,C6~C18的芳基,卤素;
X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~R2为氢,C1~C8直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基,卤素;
R3为C1~C8直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基;
R4为氢、C1~C8直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基,C6~C12的芳基,卤素;
X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~R2优选为甲基、叔丁基、枯基、三苯甲基或卤素;R3优选为为甲基、乙基、异丙基、正丁基、叔丁基、正己基、环戊基、环己基、正辛基、环辛基、苄基、苯乙基;R4优选为氢、甲基、乙基、异丙基、正丁基、叔丁基、正己基、环戊基、环己基、苯基、苄基、苯乙基、氯;X优选为二(三甲基硅)氨基。
优选的含2-取代噻唑-4-基的氨基酚类配体,其结构式如下:
优选的含2-取代噻唑-4-基的氨基酚类配体的金属锌络合物结构为:
本发明的含2-取代噻唑-4-基的氨基酚类配体(I)及其锌络合物(II)制备方法如下所示:
将4-氯甲基-2-取代噻唑与伯胺反应生成相应仲胺化合物,再加入2-溴甲基-4,6-二取代苯酚(III),反应温度为25~150℃,反应时间为2~72小时,然后从反应产物中收集配体化合物(I);
任选的,再将式(I)所示的含2-取代噻唑-4-基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2-取代噻唑-4-基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、X与满足前述的含2-取代噻唑-4-基的氨基酚类配体(I)及其金属锌络合物(II)的各相应基团一致;
锌金属原料化合物具有通式ZnX2,X与满足前述的含2-取代噻唑-4-基的氨基酚氧基锌络合物(II)的相应基团一致;更特征的,锌金属原料化合物为二{二(三甲基硅)氨基}锌。
含2-取代噻唑-4-基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。
本发明所述的含2-取代噻唑-4-基的氨基酚类配体(I)的制备方法中,4-氯甲基-2-取代噻唑的合成可参考文献方法按以下路线进行合成:
其中,将取代的硫代酰胺和1,3-二氯丙酮用无水乙醇溶解后加热回流,分离提纯得到目标化合物(Heterocycl.Commun.,2017,23(6):455–460)。
本发明所述含2-取代噻唑-4-基的氨基酚类配体(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得到(Inorg.Chem.,2002,41,3656;J.Org.Chem.,1994,59,1939):
本发明所述的含2-取代噻唑-4-基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。
以本发明所述的含2-取代噻唑-4-基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-40~110℃;聚合时催化剂与单体摩尔比为1:1~20000,优选为1:100~1000。
以本发明所述的含2-取代噻唑-4-基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-40~110℃;聚合时催化剂与醇以及单体摩尔比为1:1~50:1~20000,优选为1:1~50:100~10000;所述的醇为C1~C10直链、支链或环状结构的烷基醇,C7~C20的单或多芳基取代烷基醇。
以本发明所述的含2-取代噻唑-4-基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的单或多芳基取代烷基醇。
本发明提供的催化剂制备简单方便,在聚合过程中性质稳定,有很高的催化活性,较高等规立体选择性,对醇的耐受性好,有着广泛的应用前景。下面通过实例进一步说明本发明,但本发明不限于此。
具体实施方式
实施例1
配体L1H的合成:
(1)N-[(2-苯基噻唑-4-基)甲基]正己胺的合成
将2-苯基-4-氯甲基噻唑(10.7mmol,2.24g)溶解于30mL干燥的DMF中,加入正己胺(107mmol,14mL),最后加入无水K2CO3(11.8mmol,1.63g),搅拌反应过夜。用水淬灭反应,用乙酸乙酯萃取,有机相用饱和食盐水洗,再用无水硫酸钠干燥,旋除溶剂得到黄色油状混合物,在减压下110℃/8mmHg除去过量的正己胺,得棕红色透明油状液体的粗品。
纯度大于95%,产率约80%
(2)配体L1H的合成
在100mL的圆底烧瓶中加入上述仲胺(2.35g,约8.56mmol),无水K2CO3(1.3g,9.4mmol),用30mL DMF溶解,加入2-溴甲基-4-甲基-6-三苯甲基苯酚(4.2g,9.0mmol),室温下搅拌反应过夜。反应液用水淬灭,用二氯甲烷萃取,合并有机相,有机相再用饱和食盐水洗涤,用硫酸钠干燥,滤液在真空下浓缩除去溶剂,用石油醚重结晶,得白色固体(3.1g,产率55%)。
1H NMR(400MHz,CDCl3):δ10.81(br s,1H,OH),7.87(m,3H,ArH),7.40(m,2H,ArH),7.25–7.11(m,15H,ArH),6.90(d,4J=1.6Hz,1H,ArH),6.79(d,4J=1.6Hz,1H,ArH),6.47(s,1H,C=CHS),3.77(s,2H,ArCH2N),3.65(s,2H,NCH2C=N),2.39(t,3J=8.0Hz,2H,NCH2 ofn-hexyl),2.17(s,3H,ArCH3),1.40(m,2H,NCH2CH2),1.27–1.20(m,2H,CH2 of n-hexyl),1.14–1.06(m,2H,CH2 of n-hexyl),0.84(t,3J=8.0Hz,3H,CH3 of n-hexyl).13C{1H}NMR(100MHz,CDCl3):δ167.4(SC=N),154.3,153.5,146.3,133.8,131.3,130.8,130.0,128.9,127.1,126.6,125.5,122.4,117.2(all Ar-C),63.4(Ph3C),58.3(ArCH2),53.2(NCH2CH2),51.8(NCH2C=N),31.7(CH2 of n-hexyl),27.1(CH2 of n-hexyl),26.1(CH2 of n-hexyl),22.7(CH2 of n-hexyl),21.1(ArCH3),14.2(CH2CH3).Anal.Calcd.for C43H44N2OS:C,81.09;H,6.69;N,4.40.Found:C,80.93;H,6.98;N,4.37%.
实施例2
配体L2H的合成
(1)N-[(2-苯基噻唑-4-基)甲基]苄胺的合成
除原料采用苄胺(21.8mL,200mmol)、碳酸钾(3.0g,22mmol)和2-苯基-4-氯甲基噻唑(4.2g,20mmol)外,其它操作步骤同实施例1。在减压加热条件下(100℃/8mmHg)除去过量的苄胺,得4.5g棕红色透明液体,为产物粗品,纯度大于95%,产率约80%。
(2)配体L2H的合成
除原料采用N-[(2-苯基噻唑-4-基)甲基]苄胺(4.48g,约16mmol)、无水碳酸钾(2.43g,17.6mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(7.54g,17mmol)外,其他操作同实施例1,用二氯甲烷和甲醇重结晶,得白色固体粉末(5.9g,57%)。
1H NMR(400MHz,CDCl3):δ10.57(br s,1H,OH),7.91–7.88(m,2H,ArH),7.43–7.38(m,3H,ArH),7.25–7.11(m,18H,ArH),7.05–7.03(m,2H,ArH),6.91(d,4J=1.6Hz,1H,ArH),6.80(d,4J=1.6Hz,1H,ArH),6.66(s,1H,C=CHS),3.81(s,2H,ArCH2N),3.61(s,2H,NCH2C=N),3.54(s,2H,PhCH2N),2.17(s,3H,ArCH3).13C{1H}NMR(100MHz,CDCl3):δ167.7(SC=N),154.1,153.3,146.2,136.7,134.0,133.7,131.3,131.0,130.0,129.1,128.9,128.5,127.4,127.2,126.8,126.6,125.5,122.3,117.3(all Ar-C),63.4(Ph3C),58.1(ArCH2),56.7(PhCH2),51.2(NCH2C=N),21.0(ArCH3).Anal.Calcd.for C44H38N2OS:C,82.21;H,5.96;N,4.36.Found:C,81.91;H,6.02;N,4.31%.
实施例3
配体L3H的合成
(1)N-[(2-叔丁基噻唑-4-基)甲基]正己胺的合成
除原料采用正己胺(21.0mL,164mmol)、碳酸钾(2.5g,18mmol)和2-叔丁基-4-氯甲基噻唑(3.12g,16.4mmol)外,其它操作步骤同实施例1。在减压加热条件下(110℃/8mmHg)除去过量的正己胺,得3.0g棕红色透明油状物,纯度大于95%,产率约71%。
(2)配体L3H的合成
除原料采用N-[(2-叔丁基噻唑-4-基)甲基]正己胺(3.0g,约11.7mmol,)、无水碳酸钾(1.8g,12.9mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(5.3g,12.0mmol)外,其他操作同实施例1,用石油醚和甲醇重结晶,得白色固体(5.2g,73%)。
1H NMR(400MHz,CDCl3):δ10.84(br s,1H,OH),7.24–7.11(m,15H,ArH),6.88(d,4J=1.6Hz,1H,ArH),6.77(s,4J=1.6Hz,1H,ArH),6.37(s,1H,C=CHS),3.71(s,2H,ArCH2N)),3.58(s,2H,NCH2C=N),2.33(t,3J=8.0Hz,2H,NCH2 of n-hexyl),2.17(s,3H,ArCH3),1.39–1.33(m,2H,CH2 of n-hexyl),1.36(s,9H,(CH3)3),1.27–1.13(m,4H,CH2 of n-hexyl),1.08(m,2H,CH2 of n-hexyl),0.85(t,3J=6.8Hz,3H,CH3 of n-hexyl).13C{1H}NMR(100MHz,CDCl3):δ180.4(SC=N),154.4,151.6,146.3,133.9,131.3,130.7,128.8,127.1,126.6,125.4,122.5,115.6(all Ar-C),63.3(Ph3C),58.3(ArCH2),53.1(NCH2C=N),51.8(NCH2CH2),37.6(C(CH3)3),31.7(C(CH3)3),31.0(CH2 of n-hexyl),27.1(CH2 of n-hexyl),26.1(CH2 of n-hexyl),22.7(CH2 of n-hexyl),21.1(ArCH3),14.2(CH3 of n-hexyl).Anal.Calcd.for C41H48N2OS:C,79.83;H,7.84;N,4.54.Found:C,80.13;H,7.71;N,4.19%.
实施例4
配体L4H的合成
(1)N-[(2-叔丁基噻唑-4-基)甲基]环己胺的合成
除原料采用环己胺(18.4mL,160mmol)、碳酸钾(2.43g,17.6mmol)和2-叔丁基-4-氯甲基噻唑(3.0g,16mmol)外,其它操作步骤同实施例1。在减压加热条件下(105℃/8mmHg),除去过量的环己胺,得3.1g棕红色透明油状物,纯度大于95%,产率约77%。
(2)配体L4H的合成
除原料采用N-[(2-叔丁基噻唑-4-基)甲基]环己胺(3.1g,约12.3mmol)、无水碳酸钾(1.87g,13.5mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(5.55g,12.5mmol)外,其他操作同实施例1,用石油醚和甲醇重结晶,得白色固体(5.1g,68%)。
1H NMR(400MHz,CDCl3):δ11.00(br s,1H,OH),7.25–7.10(m,15H,ArH),6.87(s,1H,ArH),6.75(s,1H,ArH),6.36(s,1H,C=CHS),3.79(s,2H,ArCH2N),3.63(s,2H,NCH2C=N),2.44(tt,3J=11.2,2.5Hz,1H,NCH of cyclohexyl),2.17(s,3H,ArCH3),1.71(t,3J=14.6Hz,4H,CH2 of cyclohexyl),1.58(br d,3J=10.0Hz,1H,CH2 of cyclohexyl),1.34(s,9H,(CH3)3),1.26–0.95(m,5H,CH2 of cyclohexyl).13C{1H}NMR(100MHz,CDCl3):δ180.5(SC=N),154.5,153.0,146.3,133.8,131.3,130.5,128.7,127.0,126.3,125.4,122.5,115.0(all Ar-C),63.3(Ph3C),58.4(ArCH2),53.6(NCH2C=N),49.2(NCH),37.5(C(CH3)3),31.0(C(CH3)3),27.8(CH2 of cyclohexyl),26.3(CH2 of cyclohexyl),26.1(CH2 ofcyclohexyl),21.1(ArCH3).Anal.Calcd.for C41H46N2OS:C,80.09;H,7.54;N,4.56.Found:C,79.93;H,7.56;N,4.52%.
实施例5
配体L5H的合成
(1)N-[(2-苄基噻唑-4-基)甲基]正己胺的合成
除原料采用正己胺(22.0mL,166mmol)、碳酸钾(2.50g,18.3mmol)和2-苄基-4-氯甲基噻唑(3.70g,16.6mmol)外,其它操作步骤同实施例1。在减压加热条件下(105℃/8mmHg),除去过量的正己胺,得3.6g浅黄色透明油状物,纯度大于98%,产率约75%。
(2)配体L5H的合成
除原料采用N-[(2-苄基噻唑-4-基)甲基]正己胺(3.60g,约12.5mmol)、无水碳酸钾(1.89g,13.7mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(12.4mmol,5.5g)外,其他操作同实施例1,用二氯甲烷和甲醇重结晶,得白色固体(4.40g,54%)。
1H NMR(400MHz,CDCl3):δ10.81(br s,1H,OH),7.36–7.26(m,5H,ArH),7.24–7.09(m,15H,ArH),6.89(s,1H,ArH),6.77(s,1H,ArH),6.31(s,1H,C=CHS),4.24(s,2H,PhCH2),3.73(s,2H,ArCH2N),3.57(s,2H,NCH2C=N),2.35(t,3J=8.0Hz,2H,NCH2 of n-hexyl),2.17(s,3H,ArCH3),1.42–1.31(m,2H,CH2 of n-hexyl),1.28–1.12(m,4H,CH2 of n-hexyl),1.12–1.04(m,2H,CH2 of n-hexyl),0.85(t,3J=6.8Hz,3H,CH3 of n-hexyl).13C{1H}NMR(100MHz,CDCl3):δ169.5(SC=N),154.3,152.2,146.2,138.0,133.9,131.3,130.7,129.1,128.8,127.2,127.1,126.7,125.5,122.3,117.5(all Ar-C),63.3(Ph3C),58.2(ArCH2),53.3(NCH2C=N),51.9(NCH2CH2),39.6(PhCH2N),31.7(CH2 of n-hexyl),27.1(CH2of n-hexyl),26.1(CH2 of n-hexyl),22.7(CH2 of n-hexyl),21.1(ArCH3),14.2(CH3 ofn-hexyl).Anal.Calcd.for C44H46N2OS:C,81.19;H,7.12;N,4.30.Found:C,81.12;H,6.92;N,4.07%.
实施例6
配体L6H的合成
(1)N-[(2-苄基噻唑-4-基)甲基]环己胺的合成
除原料采用环己胺(19mL,166mmol)、碳酸钾(2.52g,18mmol)和2-苄基-4-氯甲基噻唑(3.7g,16.6mmol)外,其他操作步骤同实施例1。得棕色油状物,纯度大于96%,产率约86%。
(2)配体L6H的合成
除原料采用N-[(2-苄基噻唑-4-基)甲基]环己胺M6(2.8g,约9.8mmol)、无水碳酸钾(1.49g,10.8mmol)和2-溴甲基-4-甲基-6-(三苯甲基)苯酚(4.4g,10mmol)外,其他操作同L1H的合成。用二氯甲烷和石油醚重结晶,得浅黄色固体L6H(4.5g,68%)。
1H NMR(400MHz,CDCl3):δ11.09(br s,1H,OH),7.35–7.23(m,5H,ArH),7.22–7.09(m,15H,ArH),6.87(d,4J=1.6Hz,1H,ArH),6.76(d,4J=1.6Hz,1H,ArH),6.25(s,1H,C=CHS),4.19(s,2H,PhCH2),3.78(s,2H,ArCH2N),3.63(s,2H,NCH2C=N),2.46(tt,3J=11.6,2.5Hz,1H,NCH of cyclohexyl),2.16(s,3H,ArCH3),1.77–1.67(m,4H,CH2 ofcyclohexyl),1.61–1.52(br s,1H,CH2 of cyclohexyl),1.28–0.97(m,5H,CH2 ofcyclohexyl).13C{1H}NMR(100MHz,CDCl3):δ169.5(SC=N),154.4,153.5,146.2,138.1,133.7,131.3,130.6,129.1,128.8,128.7,127.1,127.0,126.5,125.4,122.3,117.0(allAr-C),63.3(Ph3C),58.5(ArCH2),53.60(NCH2C=N),49.0(NCH),39.5(PhCH2N),27.8(CH2 ofcyclohexyl),26.2(CH2 of cyclohexyl),26.0(CH2 of cyclohexyl),21.1(ArCH3).Anal.Calcd.for C44H44N2OS:C,81.44;H,6.83;N,4.32.Found:C,81.72;H,6.84;N,4.15%.
实施例7
配体L7H的合成
(1)N-[(2-氯噻唑-4-基)甲基]环己胺的合成
除原料采用环己胺(14mL,125mmol)、碳酸钾(1.90g,13.8mmol)和2-氯-4-氯甲基噻唑(2.1g,12.5mmol)外,其他操作步骤同实施例1。得金黄色油状物,纯度大于95%,产率约98%。
(2)配体L7H的合成
除原料采用N-[(2-氯噻唑-4-基)甲基]环己胺(2.9g,约15.7mmol)、无水碳酸钾(2.39g,17.3mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(7.09g,16mmol)外,其他操作同实施例1,用二氯甲烷和石油醚,得浅黄色固体(6.77g,73%)。
1H NMR(400MHz,CDCl3):δ10.98(br s,1H,OH),7.23–7.12(m,15H,ArH),6.90(d,4J=1.2Hz,1H,ArH),6.77(d,4J=1.2Hz,1H,ArH),6.07(s,1H,C=CHS),3.80(s,2H,ArCH2),3.57(s,2H,NCH2C=N),2.45(t,3J=11.2Hz,1H,NCH of cyclohexyl),2.17(s,3H,ArCH3),1.74–1.65(m,4H,CH2 of cyclohexyl),1.60(br d,3J=11.3Hz,1H,CH2 of cyclohexyl),1.29–0.98(m,5H,CH2 of cyclohexyl).13C{1H}NMR(100MHz,CDCl3):δ154.2(SC=N),152.8,150.4,146.2,133.8,131.3,130.8,128.8,127.1,126.8,125.5,122.1,119.3(all Ar-C),63.3(Ph3C),59.0(ArCH2),53.7(NCH2C=N),48.9(NCH),27.8(CH2 of cyclohexyl),26.1(CH2 of cyclohexyl),25.9(CH2 of cyclohexyl),21.0(ArCH3).Anal.Calcd.forC37H37ClN2OS:C,74.91;H,6.29;N,4.72.Found:C,74.52;H,6.28;N,4.36%.
实施例8
配体L8H的合成
(1)N-[(2-甲基噻唑-4-基)甲基]环己胺的合成
除原料采用环己胺(20mL,180mmol)、碳酸钾(1.90g,27.5mmol)和4-氯甲基噻唑(3.7g,25mmol)外,其他操作步骤同实施例1。得金黄色油状物,纯度大于96%,产率约88%。
(2)配体L8H的合成
除原料采用N-[(2-甲基噻唑-4-基)甲基]环己胺(2.1g,约10mmol)、无水碳酸钾(1.5g,11mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(4.66g,10.5mmol)外,其他操作同实施例1,用二氯甲烷和石油醚,得浅黄色固体(6.77g,73%)。
1H NMR(400MHz,CDCl3):δ11.14(br s,1H,OH),7.24–7.10(m,15H,ArH),6.87(s,1H,ArH),6.76(s,1H,ArH),6.23(s,1H,C=CHS),3.77(s,2H,ArCH2),3.62(s,2H,NCH2C=N),2.58(s,3H,ArCH3),2.45(tt,3J=11.6,2.5Hz,1H,NCH of cyclohexyl),2.16(s,3H,ArCH3),1.79–1.65(m,4H,CH2 of cyclohexyl),1.58(br d,3J=10.3Hz,1H,CH2 ofcyclohexyl),1.28–0.96(m,5H,CH2 of cyclohexyl).13C{1H}NMR(100MHz,CDCl3):δ165.0(SC=N),154.4,153.3,146.2,133.7,131.3,130.6,128.8,127.0,126.4,125.4,122.3,116.3(all Ar-C),63.3(Ph3C),58.6(ArCH2),53.6(NCH2C=N),49.0(NCH),27.7(CH2 ofcyclohexyl),26.2(CH2 of cyclohexyl),26.0(CH2 of cyclohexyl),21.1(ArCH3),19.1(ArCH3).Anal.Calcd.for C38H40N2OS:C,79.68;H,7.04;N,4.89.Found:C,79.46;H,7.11;N,4.68%.
实施例9
配体L9H的合成
(1)N-[(噻唑-4-基)甲基]环己胺的合成
除原料采用环己胺(19mL,165mmol)、碳酸钾(2.5g,18mmol)和4-氯甲基噻唑(2.2g,16.5mmol)外,其他操作步骤同实施例1。得棕黄色油状物,纯度大于98%,产率约65%。
(2)配体L9H的合成
除原料采用N-[(噻唑-4-基)甲基]环己胺(2.1g,约10.7mmol)、无水碳酸钾(1.6g,11.8mmol)和2-溴甲基-4-甲基-6-三苯甲基苯酚(4.74g,10.7mmol)外,其他操作同实施例1,用二氯甲烷和石油醚,得黄褐色固体(4.4g,74%)。
1H NMR(400MHz,CDCl3):δ11.25(br s,1H,OH),8.60(d,4J=2.0Hz,1H,N=CHS),7.24–7.11(m,15H,ArH),6.89(d,4J=1.6Hz,1H,ArH),6.78(d,4J=1.6Hz,1H,ArH),6.34(d,4J=2.0Hz,1H,C=CHS),3.81(s,2H,ArCH2),3.70(s,2H,NCH2C=N),2.42(tt,3J=11.6,2.5Hz,1H,NCH of cyclohexyl),2.17(s,3H,ArCH3),1.73(br d,3J=10.0Hz,4H,CH2 ofcyclohexyl),1.58(br d,3J=9.6Hz,1H,CH2 of cyclohexyl),1.28–1.17(m,2H,CH2 ofcyclohexyl),1.15–0.99(m,3H,CH2 of cyclohexyl).13C{1H}NMR(100MHz,CDCl3):δ154.6(SC=N),154.4,151.9,146.2,133.8,131.3,130.7,128.8,127.1,126.6,125.5,122.2,117.2(all Ar-C),63.3(Ph3C),58.6(ArCH2),53.7(NCH2C=N),48.8(NCH),27.8(CH2 ofcyclohexyl),26.2(CH2 of cyclohexyl),26.2(CH2 of cyclohexyl),21.1(ArCH3).Anal.Calcd.for C37H38N2OS:C,79.53;H,6.85;N,5.01.Found:C,79.62;H,6.89;N,4.67%.
实施例10
锌络合物Zn1的合成
在氩气氛围保护下,称取Zn[N(SiMe3)2]2(386mg,1.00mmol)加入50mL Schlenk瓶,用20mL干燥甲苯溶解,再缓慢加入配体L1H(637mg,1.00mmol),室温下搅拌反应过夜,过滤除去不溶杂质,加热浓缩成热饱和溶液,冷却重结晶。过滤后收集固体,减压下抽干,得白色固体Zn1(448mg,52.0%)。
1H NMR(400MHz,C6D6):δ7.48(d,3J=7.6Hz,6H,PhH),7.41–7.37(m,2H,ArH),7.29(d,4J=2.0Hz,1H,ArH),7.15–6.97(m,3H of ArH and 5H×0.7of toluene),6.91(t,3J=7.6Hz,6H,PhH),6.83–6.75(m,4H,ArH),5.91(s,1H,C=CHS),4.63(d,2J=12.8Hz,1H,ArCH2),3.73(d,2J=15.2Hz,1H,NCH2C=N),3.11(d,2J=12.8Hz,1H,ArCH2),2.88(td,3J=12.4Hz,2J=4.0Hz,1H,NCH2CH2),2.51(d,2J=15.2Hz,1H,NCH2C=N),2.27(s,3H,ArCH3),2.29–2.18(m,1H,NCH2CH2,overlappped with previous one),2.11(s,3H×0.7,toluene),1.98–1.84(m,1H,CH2 of n-hexyl),1.47–1.34(m,1H,CH2 of n-hexyl),1.32–1.13(m,5H,CH2 of n-hexyl),1.10–0.97(m,1H,CH2 of n-hexyl),0.89(t,3J=6.8Hz,3H,CH3 of n-hexyl),0.20–-0.26(br s,18H,N(Si(CH3)3)).13C{1H}NMR(100MHz,C6D6):δ172.5(SC=N),163.2,153.7,148.3,137.6,133.9,132.1,131.9,131.6,130.6,129.4(toluene),128.6(toluene),127.2,125.2,120.9,120.6,113.9(all Ar-C),64.2(Ph3C),59.8(ArCH2),57.8(NCH2CH2),49.8(NCH2C=N),31.9(CH2 of n-hexyl),27.6(CH2 of n-hexyl),23.3(CH2 ofn-hexyl),23.1(CH2 of n-hexyl),21.10(toluene),21.08(ArCH3),14.3(CH3 of n-hexyl),5.8(Si(CH3)3).Anal.Calcd.for C49H61N3OSSi2Zn·0.7C7H8:C,69.90;H,7.25;N,4.54.Found:C,69.37;H,7.25;N,4.39%.
实施例11
锌络合物Zn2的合成
氩气氛围保护下,称取Zn[N(SiMe3)2]2(386mg,1.00mmol)加入50mL Schlenk瓶,用约10mL干燥甲苯溶解,再缓慢加入配体L2H(642mg,1.00mmol),用少量甲苯冲洗瓶壁上的配体,共约20mL反应液,室温下搅拌反应过夜,过滤除去不溶杂质,50℃下加热浓缩成热饱和溶液,室温下冷却重结晶,过滤后收集固体,减压下抽干,得白色固体Zn2(365mg,42.1%)。
1H NMR(400MHz,C6D6):δ7.48(pesudo d,3J=7.6Hz,8H,ArH),7.28(d,4J=1.6Hz,1H,ArH),7.15–7.01(m,6H,ArH),6.90–6.80(m,8H,ArH),6.79(t,3J=7.2Hz,3H,ArH),6.54(d,4J=1.6Hz,1H,ArH),5.92(s,1H,C=CHS),4.58(d,2J=12.8Hz,1H,ArCH2),4.15(d,2J=14.3Hz,1H,PhCH2),3.92(d,2J=14.3Hz,1H,PhCH2),3.52(d,2J=12.8Hz,1H,ArCH2),3.46(d,2J=15.6Hz,1H,NCH2C=N),3.02(d,2J=15.6Hz,1H,NCH2C=N),2.09(s,3H,ArCH3),0.34–-0.15(br s,18H,N(Si(CH3)3)).13C{1H}NMR(100MHz,C6D6):δ172.7(SC=N),163.6,153.5,148.2,137.7,133.8,132.3,131.9,131.6,131.2,130.9,129.4,128.9,127.2,125.1,120.6,120.2,114.3(all Ar-C),64.2(Ph3C),58.6(ArCH2),57.9(PhCH2),45.0(NCH2C=N),20.9(ArCH3),6.1(N(Si(CH3)3)).Anal.Calcd.for C50H55N3OSSi2Zn:C,69.22;H,6.39;N,4.84.Found:C,68.98;H,6.30;N,4.65%.
实施例12
锌络合物Zn3的合成
氩气氛围保护下,称取Zn[N(SiMe3)2]2(386mg,1.00mmol)加入50mL Schlenk瓶,用约10mL无水甲苯溶解。再缓慢滴加10mL配体L3H(617mg,1.00mmol)的甲苯溶液,室温下搅拌反应过夜。过滤除去不溶杂质,在50℃下加热浓缩成约3mL的热饱和溶液,室温下冷却结晶。过滤后收集固体,减压下抽干,得白色固体Zn3(379mg,45.0%)。
1H NMR(400MHz,C6D6):δ7.47(d,3J=7.2Hz,6H,ArH),7.34(d,4J=2.0Hz,1H,ArH),7.15–7.10(m,2H×0.7of toluene),7.06–6.90(m,9H of ArH and 3H×0.7of toluene),6.80(d,4J=2.0Hz,1H,ArH),6.03(s,1H,C=CHS),4.00(d,2J=13.2Hz,1H,ArCH2),3.62(d,2J=14.8Hz,1H,NCH2C=N),3.42(d,2J=13.2Hz,1H,ArCH2),3.05(d,2J=14.8Hz,1H,NCH2C=N),3.08–2.95(m,1H,NCH2CH2,overlappped with previous signal),2.69(td,3J=13.1,2J=3.5Hz,1H,NCH2CH2),2.25(s,3H,ArCH3),2.11(s,3H×0.7,toluene),1.64–1.53(m,1H,CH2 of n-hexyl),1.32–1.17(m,7H,CH2 of n-hexyl),1.12(s,9H of C(CH3)3),0.90(t,3J=6.4Hz,3H,CH3 of n-hexyl),0.08(s,18H,N(Si(CH3)3)).13C{1H}NMR(100MHz,C6D6):δ186.0(SC=N),164.5,151.3,148.1,137.9,135.8,133.8,131.5,129.3(toluene),128.6(toluene),127.2,125.7(toluene),125.4,120.6,120.4,114.5(all Ar-C),64.2(Ph3C),57.5(ArCH2),54.6(NCH2CH2),48.9(NCH2C=N),38.3(C(CH3)3),32.0(ArC(CH3)3),31.5(CH2 of n-hexyl),27.4(CH2 of n-hexyl),23.0(CH2 of n-hexyl),21.4(ArCH3),21.1(toluene),20.8(CH2 of n-hexyl),14.3(CH3 of n-hexyl),6.5(N(Si(CH3)3)).Anal.Calcd.for C50H55N3OSSi2Zn·0.7C7H8:C,68.79;H,7.85;N,4.64.Found:C,68.37;H,7.73;N,4.49%.
实施例13
锌络合物Zn4的合成
氩气氛围保护下,称取Zn[N(SiMe3)2]2(386mg,1.00mmol)加入50mL Schlenk瓶,用约5mL甲苯溶解。再将配体L4H(615mg,1.00mmol)用约20mL甲苯溶解,缓慢滴加至前述反应瓶中,室温下搅拌反应过夜。过滤除去不溶性杂质,加热浓缩成热饱和溶液,室温冷却结晶。过滤后收集固体,减压下抽干,得白色固体Zn4(395mg,47.0%)。
1H NMR(400MHz,C6D6):δ7.47(d,3J=7.3Hz,6H,ArH),7.28(d,4J=2.4Hz,1H,ArH),7.03(t,3J=7.3Hz,6H,ArH),6.95(t,3J=7.3Hz,3H,ArH),6.74(d,4J=2.4Hz,1H,ArH),6.02(s,1H,C=CHS),3.83(d,2J=12.8Hz,1H,ArCH2),3.39(d,2J=14.8Hz,1H,NCH2C=N),3.32(d,2J=12.8Hz,1H,ArCH2),3.31(d,2J=14.8Hz,1H,NCH2C=N),2.85(t,3J=9.6Hz,1H,NCH of cyclohexyl),2.55(br s,1H,CH2 of cyclohexyl),2.23(s,3H,ArCH3),2.04(br d,3J=10.4Hz,1H,CH2 of cyclohexyl),1.70(br d,3J=11.2Hz,2H,CH2 of cyclohexyl),1.44(br d,3J=12.0Hz,1H,CH2 of cyclohexyl),1.21–0.86(m,5H of CH2 ofcyclohexyl),1.14(s,9H,C(CH3)3),0.09(s,18H,N(Si(CH3)3)).13C{1H}NMR(100MHz,C6D6):δ186.67(SC=N),164.7,151.0,148.4,135.4,134.4,131.9,131.1,127.4,125.4,121.1,120.6,114.5(all Ar-C),64.2(Ph3C),61.2(ArCH2),55.2(NCH),48.2(NCH2C=N),38.4(C(CH3)3),31.9(C(CH3)3),28.6(CH2 of cyclohexyl),26.5(CH2 of cyclohexyl),26.3(CH2of cyclohexyl),26.1(CH2 of cyclohexyl),25.6(CH2 of cyclohexyl),21.0(ArCH3),6.4(N(Si(CH3)3)).Anal.Calcd.for C47H63N3OSSi2Zn:C,67.23;H,7.56;N,5.00.Found:C,67.20;H,7.50;N,5.05%.
实施例14
锌络合物Zn5的合成
氩气氛围保护下,称取Zn[N(SiMe3)2]2(386mg,1.00mmol)加入50mL Schlenk瓶中,用约10mL干燥甲苯溶解,再分批缓慢加入配体L5H(651mg,1.00mmol),用少量甲苯冲洗瓶壁,共约20mL反应溶液,室温下搅拌反应过夜,过滤除去不溶性杂质,加热浓缩成约4mL热饱和溶液,冷却结晶,过滤后收集固体,减压下抽干,得橙黄色固体Zn5(377mg,43.8%)。
1H NMR(400MHz,C6D6):δ7.49(d,3J=7.2Hz,6H,PhH),7.36(d,3J=6.8Hz,2H,ArH),7.25(d,4J=2.0Hz,1H,ArH),7.21–7.10(m,3H,ArH,overlapped with the signal ofC6D6),7.02(pesudo t,3J=7.3Hz,6H,PhH),6.96(t,3J=7.0Hz,3H,PhH),6.73(d,4J=2.0Hz,1H,ArH),5.69(s,1H,C=CHS),4.55(d,2J=12.4Hz,1H,ArCH2),4.40(d,2J=18.2Hz,1H,PhCH2),3.84(d,2J=18.2Hz,1H,PhCH2),3.56(d,2J=15.2Hz,1H,NCH2C=N),2.97(d,2J=12.4Hz,1H,ArCH2),2.76(td,3J=12.4,2J=3.6Hz,1H,NCH2CH2),2.41(d,2J=15.2Hz,1H,NCH2C=N),2.24(s,3H,ArCH3),2.15(td,3J=12.4Hz,2J=4.8Hz,1H,NCH2CH2),1.95–1.82(m,1H,CH2 of n-hexyl),1.49–1.39(m,1H,CH2 of n-hexyl),1.29–1.18(m,5H of CH2 ofn-hexyl and 8H×0.5of C6H14),1.10–0.98(m,1H,CH2 of n-hexyl),0.96–0.87(m,3H ofCH3 of n-hexyl and 6H×0.5of C6H14),0.19(s,18H,N(Si(CH3)3)).13C{1H}NMR(100MHz,C6D6):δ177.5(SC=N),163.6,152.5,148.4,137.3,136.1,131.9,131.7,130.0,129.5,129.0,127.1,125.2,121.8,121.2,120.5,114.5(all Ar-C),64.2(Ph3C),60.2(PhCH2),60.0(ArCH2),58.5(NCH2CH2),48.0(NCH2C=N),32.0(CH2 of n-hexyl),31.9(n-hexane),27.6(CH2 of n-hexyl),23.1(CH2 of n-hexyl),23.0(n-hexane),21.1(ArCH3),21.0(CH2of n-hexyl),14.4(CH3 of n-hexyl),14.3(n-hexane),6.2(N(Si(CH3)3)).Anal.Calcd.for C50H63N3OSSi2Zn·0.5C6H14:C,69.49;H,7.63;N,4.54.Found:C,69.37;H,7.09;N,4.25%.
实施例15
锌络合物Zn6的合成
氩气氛围保护下,称取Zn[N(SiMe3)2]2(386mg,1.00mmol)加入50mL Schlenk瓶,用约5mL甲苯溶解。再缓慢加入配体L6H(648mg,1.00mmol),用少量甲苯冲洗瓶壁,共约10mL反应溶液,室温下搅拌反应过夜。过滤除去不溶性杂质,加热浓缩成约2mL热饱和溶液,冷却后析出较少晶体,再加入正己烷重结晶。过滤后收集固体,减压下将固体抽干,得浅黄色固体Zn6(533mg,61.0%)。
1H NMR(400MHz,C6D6):δ7.54(d,3J=7.6Hz,6H,ArH),7.34(d,3J=6.8Hz,2H,ArH),7.28(d,4J=2.0Hz,1H,ArH),7.21–7.10(m,5H of ArH and 2H×0.5of toluene,overlapped with the signal of C6D6),7.08–7.01(m,6H of ArH and 3H×0.5oftoluene),6.95(t,3J=7.2Hz,3H,ArH),6.70(d,4J=2.0Hz,1H,ArH),5.65(s,1H,C=CHS),4.42(d,2J=12.3Hz,1H,ArCH2),4.35(d,2J=18.1Hz,1H,PhCH2),3.66(d,2J=18.1Hz,1H,PhCH2),3.37(d,2J=15.6Hz,1H,NCH2C=N),3.14(d,2J=12.3Hz,1H,ArCH2),2.91(br d,2J=15.6Hz,1H,NCH2C=N),2.69(br d,3J=12.8Hz,1H,CH2 of cyclohexyl),2.56(t,3J=11.2Hz,1H,NCH of cyclohexyl),2.25(s,3H,ArCH3),2.11(s,3H×0.5,toluene),1.74–1.59(m,3H,CH2 of cyclohexyl),1.49–1.40(m,1H,CH2 of cyclohexyl),1.34–1.01(m,3H,CH2 of cyclohexyl),0.96–0.87(m,2H,CH2 of cyclohexyl),0.24(s,18H,N(Si(CH3)3)).13C{1H}NMR(100MHz,C6D6):δ177.4(SC=N),164.0,152.7,148.5,137.9(toluene),136.5,136.3,133.6,131.8,131.3,130.1,129.5,129.3(toluene),128.6(toluene),127.2,125.7(toluene),125.2,121.7,120.4,113.2(all Ar-C),64.1(Ph3C),61.9(ArCH2),61.8(PhCH2),54.5(NCH),46.6(NCH2C=N),38.3(CH2 of cyclohexyl),30.3(CH2 ofcyclohexyl),26.7(CH2 of cyclohexyl),26.1(CH2 of cyclohexyl),23.4(CH2 ofcyclohexyl),21.1(toluene),21.0(ArCH3),6.1(N(Si(CH3)3)).Anal.Calcd.forC50H61N3OSSi2Zn·0.5C7H8:C,69.87;H,7.12;N,4.57.Found:C,69.71;H,7.01;N,4.54%.
实施例16
锌络合物Zn7的合成
氩气氛围保护下,称取Zn[N(SiMe3)2]2(386mg,1.00mmol)加入50mL Schlenk瓶,用约10mL甲苯溶解。再缓慢加入配体L7H(593mg,1.00mmol),室温下搅拌反应过夜后,析出大量白色固体。过滤后收集固体,减压下抽干,得白色固体Zn7(706mg,86.3%)。
1H NMR(400MHz,C6D6):δ7.49(d,3J=7.6Hz,6H,ArH),7.34(d,4J=2.0Hz,1H,ArH),7.13(m,2H×0.6of toluene,ArH),7.06–6.97(m,6H of ArH and 3H×0.6of toluene,ArH),6.88(t,3J=7.2Hz,3H,ArH),6.71(d,4J=2.0Hz,1H,ArH),5.44(s,1H,C=CHS),4.42(d,2J=12.4Hz,1H,ArCH2),3.12(d,2J=15.6Hz,1H,NCH2C=N),3.07(d,2J=12.4Hz,1H,ArCH2),2.80(br d,3J=11.6Hz,1H,CH2 of cyclohexyl),2.58(d,2J=15.6Hz,1H,NCH2C=N),2.39(t,3J=11.2Hz,1H,NCH of cyclohexyl),2.25(s,3H,ArCH3),2.11(s,1.8H,3H×0.6of toluene),1.72–1.58(m,2H,CH2 of cyclohexyl),1.41(br d,3J=8.4Hz,2H,CH2 ofcyclohexyl),1.29–0.76(m,5H,CH2 of cyclohexyl),0.21(s,18H,N(Si(CH3)3)).13C{1H}NMR(100MHz,C6D6):δ163.2(SC=N),156.6,151.9,148.2,137.9(toluene),137.7,133.5,131.8,129.3,128.6(toluene),127.1,125.7(toluene),125.2,121.1,120.6,115.4(allAr-C),64.1(Ph3C),61.2(ArCH2),53.5(NCH),46.0(NCH2C=N),30.4(CH2 of cyclohexyl),26.7(CH2 of cyclohexyl),26.1(CH2 of cyclohexyl),25.9(CH2 of cyclohexyl),22.6(CH2 of cyclohexyl),21.4(ArCH3),21.1(toluene),5.9(N(Si(CH3)3)).Anal.Calcd.forC43H54N3OSClSi2Zn·0.6C7H8:C,64.92;H,6.79;N,4.81.Found:C,64.55;H,6.80;N,4.87%.
实施例17
锌络合物Zn8的合成
氩气氛围保护下,称取Zn[N(SiMe3)2]2(386mg,1.00mmol)加入50mL Schlenk瓶,用少量无水甲苯溶解,再缓慢加入配体L8H(573mg,1.00mmol),共约10mL反应溶液,室温下反应过夜,过滤除去不溶性杂质,加热浓缩后,加入正己烷重结晶,过滤后收集固体,减压下抽干,得黄褐色固体(380mg,47.6%)。
1H NMR(400MHz,C6D6):δ7.47(d,3J=7.5Hz,6H),7.26(d,4J=2.0Hz,1H,ArH),7.15–7.12(m,2H×0.2of toluene),7.04–7.01(m,3H×0.2of toluene),6.97(t,3J=7.5Hz,6H,ArH),6.86(t,3J=7.2Hz,3H,ArH),6.74(d,4J=2.0Hz,1H,ArH),5.67(s,1H,C=CHS),4.42(d,2J=12.4Hz,1H,ArCH2),3.28(d,2J=15.2Hz,1H,NCH2C=N),3.12(d,2J=12.4Hz,1H,ArCH2),2.77(d,2J=15.2Hz,1H,NCH2C=N),2.77(br d,1H,CH2 ofcyclohexyl,overlappped with previous signal),2.45(tt,3J=11.6,2J=3.5Hz,1H,NCHof cyclohexyl),2.25(s,3H,ArCH3),2.11(s,3H,ArCH3),2.10(s,1.8H,3H×0.2oftoluene),1.73–1.58(m,2H,CH2 of cyclohexyl),1.52–1.39(m,2H,CH2 of cyclohexyl),1.32–1.20(m,1H,CH2 of cyclohexyl),1.16–0.99(m,2H,CH2of cyclohexyl),0.93–0.80(m,2H,CH2 of cyclohexyl),0.17(s,18H,N(Si(CH3)3)).13C{1H}NMR(100MHz,C6D6):δ170.6(SC=N),163.7,151.9,148.3,137.9(toluene),137.2,131.9,130.2,129.3(toluene),128.6(toluene),127.0,125.7(toluene),125.2,121.5,120.4 115.4(all Ar-C),64.1(Ph3C),61.3(ArCH2),53.8(NCH),46.2(NCH2C=N),30.6(CH2 of cyclohexyl),26.8(CH2 ofcyclohexyl),26.2(CH2 of cyclohexyl),26.0(CH2 of cyclohexyl),22.7(CH2 ofcyclohexyl),21.4(ArCH3)21.1(toluene),19.8(ArCH3),5.9(N(Si(CH3)3)).Anal.Calcd.for C44H57N3OSSi2Zn·0.2C7H8:C,66.83;H,7.24;N,5.15.Found:C,66.54;H,7.11;N,4.77%.
实施例18
锌络合物Zn9的合成
氩气氛围保护下,称取Zn[N(SiMe3)2]2(386mg,1mmol)加入50mL Schlenk瓶,用少量无水甲苯溶解,再缓慢加入配体L9H(559mg,1mmol),共约10mL反应溶液,室温下反应过夜,过滤除去不溶性杂质,加热浓缩后,加入正己烷重结晶,过滤后收集固体,减压下抽除溶剂和反应生成的自由硅胺,得黄褐色固体(262mg,43%)。
1H NMR(400MHz,C6D6):δ7.69(d,3J=7.6Hz,6H,ArH),7.23–7.17(m,7H,ArH),7.13(m,2H×0.3of toluene),7.07–7.00(m,3H×0.3of toluene),6.96(t,3J=7.6Hz,3H,ArH),6.32(d,4J=2.0Hz,1H,ArH),6.17(d,4J=2.0Hz,1H,ArH),5.53(s,1H,C=CHS),3.98(d,J=11.2Hz,1H,ArCH2),3.21(d,J=15.2Hz,1H,NCH2C=N),2.96(d,J=15.2Hz,1H,NCH2C=N),2.92(d,J=11.2Hz,1H,ArCH2),2.73(tt,3J=11.6,3.5Hz,1H,NCH of cyclohexyl),2.29–2.20(m,2H,CH2 of cyclohexyl),2.11(s,3H of ArCH3,overlapped 3H×0.3oftoluene),1.69(br d,3J=12.8Hz,2H,CH2 of cyclohexyl),1.49(br d,3J=12.8Hz,1H,CH2 of cyclohexyl),1.20–1.07(m,2H,CH2 of cyclohexyl),1.01–0.83(m,3H,CH2 ofcyclohexyl),0.27(s,18H,N(Si(CH3)3)).13C{1H}NMR(100MHz,C6D6):δ164.7(SC=N),156.2,152.3,148.0,137.9(toluene),133.1,132.2,131.7,130.3,129.3(toluene),128.6(toluene),127.3,125.7(toluene),124.8,122.0,120.4,111.8(all Ar-C),66.8(Ph3C),63.8(ArCH2),57.8(NCH),51.9(NCH2C=N),28.5(CH2 of cyclohexyl),28.0(CH2 ofcyclohexyl),26.3(CH2 of cyclohexyl),26.2(CH2 of cyclohexyl),26.1(CH2 ofcyclohexyl),21.1(toluene),21.0(ArCH3),6.2(N(Si(CH3)3)).Anal.Calcd.forC43H55N3OSSi2Zn·0.3C7H8:C,66.78;H,7.13;N,5.18.Found:C,66.47;H,7.12;N,4.87%.
实施例19
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.00mmol),用0.5mL甲苯溶解。量取催化剂Zn5的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.002M,[Zn]0:[rac-LA]0=1:500。控制反应温度25±1℃,反应12.3小时后,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇洗涤聚合物。真空干燥24h。转化率:85%,Mn=1.48×105g/mol,分子量分布PDI=1.57,等规度Pm=0.83。
实施例20
除催化剂换成Zn5、溶剂换成四氢呋喃外,其他操作同实施实例19,反应7.3小时后,转化率:85%,Mn=1.69×105g/mol,分子量分布PDI=1.49,等规度Pm=0.80。
实施例21
除催化剂换成Zn6外,其他操作同实施实例19,反应5.6小时后,转化率:86%,Mn=1.03×105g/mol,分子量分布PDI=1.45,等规度Pm=0.78。
实施例22
除催化剂换成Zn6、溶剂换成四氢呋喃外,其他操作同实施实例19,反应8.3小时后,转化率:93%,Mn=1.37×105g/mol,分子量分布PDI=1.52,等规度Pm=0.73。
实施例23
除催化剂换成Zn7外,其他操作同实施实例19,反应5.8小时后,转化率:86%,Mn=1.35×105g/mol,分子量分布PDI=1.61,等规度Pm=0.68。
实施例24
除催化剂换成Zn8外,其他操作同实施实例19,反应8小时后,转化率:88%,Mn=1.23×105g/mol,分子量分布PDI=1.63,等规度Pm=0.79。
实施例25
除催化剂换成Zn8、溶剂换成四氢呋喃外,其他操作同实施实例19,反应50分钟后,转化率:90%,Mn=1.14×105g/mol,分子量分布PDI=1.56,等规度Pm=0.84。
实施例26
除催化剂换成Zn9外,其他操作同实施实例19,反应59分钟后,转化率:83%,Mn=1.12×105g/mol,分子量分布PDI=1.64,等规度Pm=0.80。
实施例27
除催化剂换成Zn9、溶剂换成四氢呋喃外,其他操作同实施实例19,反应50分钟后,转化率:90%,Mn=1.14×105g/mol,分子量分布PDI=1.56,等规度Pm=0.84。
实施例28
在氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.00mmol),用0.50mL异丙醇的甲苯溶液溶解。量取催化剂Zn5的甲苯溶液0.50mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.002M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:500。控制反应温度25±1℃,反应2.8小时后,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇洗涤聚合物。真空干燥24h。转化率:92%,Mn=9.03×104g/mol,分子量分布PDI=1.25,等规度Pm=0.81。
实施例29
除催化剂换成Zn5、溶剂换成四氢呋喃外,其他操作同实施实例28,反应3.3小时后,转化率:85%,Mn=7.03×104g/mol,分子量分布PDI=1.16,等规度Pm=0.80。
实施例30
除催化剂换成Zn6外,其他操作同实施实例33,其他操作同实施实例28,反应2.3小时后,转化率:90%,Mn=7.73×104g/mol,分子量分布PDI=1.14,等规度Pm=0.76。
实施例31
除催化剂换成Zn8外,其他操作同实施实例28,反应2小时后,转化率:92%,Mn=7.38×104g/mol,分子量分布PDI=1.29,等规度Pm=0.78。
实施例32
除催化剂换成Zn9外,其他操作同实施实例28,反应25分钟后,转化率:93%,Mn=9.61×104g/mol,分子量分布PDI=1.33,等规度Pm=0.80。
实施例33
除催化剂换成Zn9、溶剂换成四氢呋喃外,其他操作同实施实例28,反应35分钟后,转化率:95%,Mn=7.22×104g/mol,分子量分布PDI=1.31,等规度Pm=0.84。
实施例34
除催化剂换成Zn9、聚合温度为-20℃外,其他操作同实施实例28,反应7.0小时后,转化率:87%,Mn=8.43×104g/mol,分子量分布PDI=1.33,等规度Pm=0.89。
实施例35
除催化剂换成Zn9、聚合温度为-40℃外,其他操作同实施实例28,反应48h后,转化率:83%,Mn=8.57×104g/mol,分子量分布PDI=1.30,等规度Pm=0.92。
实施例36
在氩气氛围保护下,于10mL聚合瓶中加入外消旋丙交酯(144mg,1.00mmol),加入0.10mL的异丙醇/甲苯溶液,再加入0.10mL催化剂Zn9的甲苯溶液。保持[rac-LA]0/[Zn]0/[iPrOH]=1500:1:1。置于110±1°С油浴中搅拌,反应2.5min,加入石油醚终止聚合。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇洗涤聚合物。真空干燥24h。转化率:96%,Mn=2.38×105g/mol,分子量分布PDI=1.70,等规度Pm=0.76,TOF=34560h-1。
实施例37
催化剂仍为Zn9,除换成[rac-LA]0/[Zn]0/[iPrOH]=5000:1:1外,其他操作同实施实例36。反应18min后,转化率:97%,Mn=6.99×105g/mol(Mw=9.27×105g/mol),分子量分布PDI=1.35,等规度Pm=0.70,TOF=16167h-1。
实施例38
催化剂仍为Zn9,除换成[rac-LA]0/[Zn]0/[iPrOH]=5000:1:50外,其他操作同实施实例36。反应4min后,转化率:90%,Mn=3.63×104g/mol,分子量分布PDI=1.24,等规度Pm=0.74,TOF=67500h-1。
实施例39
催化剂仍为Zn9,除[rac-LA]0/[Zn]0/[iPrOH]=1000:1:100外,其他操作同实施实例36。反应8min后,转化率:83%,Mn=3.36×104g/mol,分子量分布PDI=1.10,等规度Pm=0.74,TOF=62250h-1。
实施例40
除聚合单体换成D-LA外,其他操作同实施实例19,反应20min后,转化率:92%,Mn=7.5×104g/mol,分子量分布PDI=1.30。
实施例41
除聚合单体换成L-LA外,其他操作同实施实例19,反应20min后,转化率:88%,Mn=7.0×104g/mol,分子量分布PDI=1.33。
实施例42
除聚合单体换成ε-己内酯外,其他操作同实施实例19,反应12min后,转化率:91%,Mn=5.10×104g/mol,分子量分布PDI=1.24。
Claims (10)
2.根据权利要求1所述的含2-取代噻唑-4-基的氨基酚类配体(I)及其金属锌络合物(II),其特征在于,R1~R2为氢,C1~C8直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基,卤素;R3为C1~C8直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基;R4为氢、C1~C8直链、支链或环状结构的烷基,C7~C20的单或多芳基取代烷基,C6~C12的芳基,卤素;X为二(三甲基硅)氨基,二(三乙基硅)氨基,二(二甲基氢硅)氨基。
3.根据权利要求1所述的含2-取代噻唑-4-基的氨基酚类配体(I)及其金属锌络合物(II),其特征在于,R1~R2为甲基、叔丁基、枯基、三苯甲基或卤素;R3为甲基、乙基、异丙基、正丁基、叔丁基、正己基、环戊基、环己基、正辛基、环辛基、苄基、苯乙基;R4为氢、甲基、乙基、异丙基、正丁基、叔丁基、正己基、环戊基、环己基、苯基、苄基、苯乙基、氯;X为二(三甲基硅)氨基。
4.权利要求1~3任一项所述的含2-取代噻唑-4-基的氨基酚类配体(I)及其金属锌络合物(II)的制备方法,包括如下步骤:
将4-氯甲基-2-取代噻唑类化合物与伯胺反应生成相应仲胺,加入2-溴甲基-4,6-二取代苯酚(III),反应温度为25~150℃,反应时间为2~72小时,然后从反应产物中收集配体化合物(I);
任选的,再将式(I)所示的含2-取代噻唑-4-基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2-取代噻唑-4-基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任一项所述的含2-取代噻唑-4-基的氨基酚类配体(I)及其金属锌络合物(II)的各相应基团一致;
锌金属原料化合物具有通式ZnX2,X与满足权利要求1~3任一项所述的含2-取代噻唑-4-基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,含2-取代噻唑-4-基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任一项所述的含2-取代噻唑-4-基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任一项所述的含2-取代噻唑-4-基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任一项所述的含2-取代噻唑-4-基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的单或多芳基取代烷基醇。
10.根据权利要求6所述的应用,其特征在于,以权利要求1~3任一项所述的含2-取代噻唑-4-基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-己内酯或β-丁内酯聚合;所述的醇为C1~C10直链、支链或环状结构的烷基醇,C7~C20的单或多芳基取代烷基醇。
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