CN111362885A - Benzothiazole ring substituted aminophenol oxygen radical zinc complex and preparation method and application thereof - Google Patents
Benzothiazole ring substituted aminophenol oxygen radical zinc complex and preparation method and application thereof Download PDFInfo
- Publication number
- CN111362885A CN111362885A CN202010153706.7A CN202010153706A CN111362885A CN 111362885 A CN111362885 A CN 111362885A CN 202010153706 A CN202010153706 A CN 202010153706A CN 111362885 A CN111362885 A CN 111362885A
- Authority
- CN
- China
- Prior art keywords
- substituted
- benzothiazole ring
- arh
- zinc complex
- lactide
- Prior art date
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- 239000011701 zinc Substances 0.000 title claims abstract description 62
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 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 9
- 238000010668 complexation reaction Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 239000003446 ligand Substances 0.000 claims abstract description 45
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- QNHGHNJBZCMVOX-UHFFFAOYSA-M N[Zn]OC1=CC=CC=C1 Chemical class N[Zn]OC1=CC=CC=C1 QNHGHNJBZCMVOX-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 8
- 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 105
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 39
- -1 triethylsilyl Chemical group 0.000 claims description 26
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- 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 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 17
- 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 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 125000004122 cyclic group Chemical group 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- SERUZNHRWBXDOX-UHFFFAOYSA-N 2-(chloromethyl)-1,3-benzothiazole Chemical compound C1=CC=C2SC(CCl)=NC2=C1 SERUZNHRWBXDOX-UHFFFAOYSA-N 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- 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 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 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 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 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
- 125000003277 amino 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
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000003141 primary amines Chemical class 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
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 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
- 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 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 30
- 238000003786 synthesis reaction Methods 0.000 abstract description 30
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 5
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 12
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 description 11
- 239000007858 starting material Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- WIMDKCGAUGHBFY-UHFFFAOYSA-N 2-(bromomethyl)-4-methyl-6-tritylphenol Chemical compound CC1=CC(CBr)=C(O)C(C(C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 WIMDKCGAUGHBFY-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920003232 aliphatic polyester Polymers 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000001704 evaporation Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- MEWFUIBAAVEAQI-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylmethyl)hexan-1-amine Chemical compound C1=CC=C2SC(CNCCCCCC)=NC2=C1 MEWFUIBAAVEAQI-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 1
- YAXGBZDYGZBRBQ-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazol-2-amine Chemical compound NC1=NCCO1 YAXGBZDYGZBRBQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- HSOHBWMXECKEKV-UHFFFAOYSA-N cyclooctanamine Chemical compound NC1CCCCCCC1 HSOHBWMXECKEKV-UHFFFAOYSA-N 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 229940117803 phenethylamine Drugs 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 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
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses benzothiazole ring-substituted aminophenol oxygen-based zinc complex, a preparation method thereof and application thereof in catalyzing ring-opening polymerization of lactone with high activity and high selectivity. The preparation method comprises the following steps: the neutral ligand directly reacts with the metal raw material compound in an organic medium, and then the target compound is obtained through the steps of filtering, concentrating and recrystallizing. The benzothiazole ring substituted aminophenoxy zinc complex of the present invention isAn efficient lactone ring-opening polymerization catalyst can be used for catalyzing the polymerization reaction of lactones such as lactide and the like; in particular for racemic lactide, a polylactide of high isotacticity is obtained. The benzothiazole ring substituted aminophenol oxygen radical zinc complex has obvious advantages: the raw materials are easy to obtain, the synthesis route is simple, the product yield is high, the catalyst activity and the stereoselectivity are very high, the high-regularity and high-molecular-weight polyester material can be obtained, and the requirements of industrial departments can be met. The structural formula is as follows:
Description
Technical Field
The invention relates to benzothiazole ring substituted aminophenol oxygen zinc complexes and application of the complexes in lactone polymerization.
Background
Petroleum-based materials are difficult to biodegrade, causing severe environmental pollution, and limited petroleum resources do not meet the strategy of sustainable development. The aliphatic polyester material has the advantages of degradability, biocompatibility and the like, wherein polylactic acid serving as a novel green material has the advantages, and meanwhile, the raw material of the aliphatic polyester material is renewable, so that the carbon cycle of the aliphatic polyester material in nature is realized, the aliphatic polyester material is a well-known environment-friendly green high polymer material, and the aliphatic polyester material is widely applied to the fields of medicines, medical treatment, food packaging and the like. With the progress of science and technology, new requirements and applications are provided for the performance of polylactic acid materials, and in order to controllably obtain polylactic acid polymers with good performance, designing and synthesizing a catalyst with high catalytic performance is the most critical factor. In which lactic acid is cyclized to form lactide, and the lactide with high molecular weight, high crystallinity, high melting point and controllable structure is obtained by catalytic polymerization with a catalyst, which attracts wide attention.
Lactide has two chiral carbons and can form three isomers, levo-Lactide (L-Lactide, L-LA), dextro-Lactide (D-Lactide, D-LA) and meso-Lactide (meso-LA); in addition, a mixture of L-and D-Lactide in equal proportions (L-Lactide: D-Lactide ═ 1:1) is called racemic Lactide (rac-Lactide, rac-LA). Catalyzing the polymerization of lactide with different configurations can obtain polylactide with various microstructures: isotactic polylactide can be obtained by catalyzing a single chiral lactide monomer; the meso-lactide monomer is catalyzed to obtain syndiotactic, hetero-regular or atactic polylactide; the random, irregular or isotactic block polylactic acid can be obtained by catalyzing racemic lactide monomer. These polylactides have different physical and mechanical properties and can be used in different fields. The isotactic block polylactide obtained by polymerizing the racemic lactide serving as a raw material has higher melting point and crystallinity, and can obviously improve the physical and mechanical properties of the polymer material. The metal zinc complex can catalyze the ring opening polymerization of the racemic lactide with high activity. In addition, zinc element has the characteristics of no color, no toxicity, biocompatibility and the like, and even trace residues in the polymer meet the application requirements of the polymer in the fields of food packaging and medicines, so that the design and synthesis of a zinc complex with high activity and high isotactic selectivity to realize the controllable synthesis of polylactide polymers becomes one of the current research hotspots.
In 1999, the Coates group used β -diimino (BDI) binuclear zinc complex (BDI) Zn (O)iPr) as catalyst for polymerizing racemic lactide with good controllability and high-purity polylactide, PrChisholm group reported zinc complexes of multidentate sites β -diimine ligands, catalyzing the polymerization of racemic lactide to give higher-tacticity polylactide, P.AmrThe research group of Hillmyer and Tolman synthesized in 2003 a bisethoxy bridged binuclear zinc complex with high catalytic activity for ring-opening polymerization of racemic lactide but no stereoselectivity (j.am.chem.soc.2003,125,11350), and the group reported a multidentate aminophenoxy zinc complex, which showed high catalytic activity for lactide polymerization, and obtained a partially isotactic polymer by adjusting the length of the carbon chain of the claw-shaped coordination site (Dalton trans.,2010,39, 7897) and 2011), and the group reported β -monophosphinoiminozinc complex with higher catalytic activity for racemic lactide polymerization but only obtained an atactic polymer (organometallalics, 2011,30,4364, 2013), and reported that the chiral aminophenoxy zinc complex achieved the first time racemic zinc complex, and the group reported that the first time polymerized the stereoselectivity Pm0.81(chem. commun.,2013,49, 8686). In 2014, the Du group reported chiral amino oxazoline-based zinc complexes with high stereoselectivity P for racemic lactide polymerizationmWhen the melting point of the obtained polymer is 0.90, T is reachedm214 ℃, but the catalyst activity was low (ACS Macro lett.2014,3,689). In 2016, Williams' group designed synthetic macrocyclic dinuclear zinc complexes to completely polymerize 1000 equivalents of racemic lactide within 1min, TOF 60000h-1But not stereoselectivity (angelw. chem. int. ed.2016,128, 1-7). 2017 and 2018, we report a series of chiral oxazoline or non-chiral benzoxazole substituted aminophenol oxygroup zinc complexes, which have higher activity and higher isotactic selectivity when catalyzing racemic lactide polymerization, and Pm＝0.89(Macromolecules,2017,50(20), 7911-7919; chem, 2018,57(17), 11240-11251). In 2019, we further report that imidazole ring-substituted aminophenol oxygen-based zinc complexes show high activity and high isotactic selectivity when catalyzing racemic lactide polymerization, and P ism＝0.89(Chem.Commun.,2019,55,10112-10115)。
Great breakthroughs are made in the research of catalyzing the polymerization of the racemic lactide, but the design of a catalyst with high activity and high isotactic selectivity is still very challenging. At present, although individual zinc complexes show high regular selectivity for ring-opening polymerization of racemic lactide, the catalyst is sensitive to water, oxygen and impurities. Therefore, the research work on the zinc complex catalyst is still going to be further advanced to synthesize and obtain a high-efficiency catalyst which integrates high activity, high isotactic selectivity and better tolerance to impurities such as water, oxygen and the like.
Disclosure of Invention
The invention aims to disclose a benzothiazole ring substituted aminophenol oxygen radical zinc complex.
The invention also discloses a preparation method of the benzothiazole ring substituted aminophenol oxygen radical zinc complex.
The invention also aims to disclose the application of the benzothiazole ring substituted aminophenol oxygen zinc complex as a catalyst in lactone polymerization.
The technical idea of the invention is as follows:
the aminophenol ligand has the characteristics of easily obtained raw materials, simple and convenient synthesis, adjustable structure and the like, the electronic effect and the steric effect are adjusted by changing the substituent, the aminophenol ligand is applied to the synthesis of the zinc complex catalyst, and the complex is applied to the catalysis of the ring-opening polymerization of the racemic lactide and has convenience and easy regulation and control. Research shows that the introduction of oxazole ring into aminophenol ligand can obtain high activity and high isotactic stereoselectivity catalyst. The invention introduces a benzothiazole ring into an aminophenoxy ligand structure, and hopefully, a novel zinc complex catalyst with soft ligand coordination can be constructed. The Lewis acidity of the metal center and the steric hindrance of the metal center are adjusted by changing the substituent on the ligand skeleton, so that the ring-opening polymerization of the racemic lactide is catalyzed by the zinc complex with high activity and high stereoselectivity, and the industrialization potential is further improved.
The benzothiazole ring substituted aminophenol ligand (I) and the metal zinc complex (II) thereof are characterized by having the following general formula:
in the formulae (I), (II):
R1～R2each represents hydrogen, C1～C20Alkyl of linear, branched or cyclic structure, C7～C30Mono-or poly-aryl-substituted alkyl of (a), halogen;
R3represents C1～C20Alkyl of linear, branched or cyclic structure, C7～C30Mono-or polyaryl-substituted alkyl of, C6～C18Aryl of (a);
x represents an amino group NR4R5Wherein R is4～R5Are respectively C1～C6Alkyl of linear, branched or cyclic structure, trimethylsilyl, triethylsilyl, dimethylhydrosilyl, R4And R5May be the same or different.
More characterized in that in the formulae (I) and (II), R1～R2Preferably hydrogen, C1～C8Alkyl of linear, branched or cyclic structure, C7～C20Mono-or poly-aryl-substituted alkyl of (a), halogen;
R3preferably C1～C8Alkyl of linear, branched or cyclic structure, C7～C20Mono-or polyaryl-substituted alkyl of, C6～C12Aryl of (a);
x is preferably di (trimethylsilyl) amino, di (triethylsilyl) amino or di (dimethylhydrosilyl) amino.
In the formulae (I), (II), R1～R2Preferably hydrogen, methyl, tert-butyl, cumylTrityl or halogen; r3Preferably methyl, ethyl, isopropyl, n-butyl, tert-butyl, n-hexyl, cyclopentyl, cyclohexyl, n-octyl, cyclooctyl, benzyl, phenethyl; x is preferably a bis (trimethylsilyl) amino group.
Preferred benzothiazole ring-substituted aminophenol ligands have the following structural formula:
preferred metal zinc complex structures of the aminophenol ligands are:
the preparation method of the benzothiazole ring substituted aminophenol ligand (I) and the zinc complex (II) thereof is as follows:
reacting 2-chloromethylbenzothiazole with primary amine to generate corresponding secondary amine, adding 2-bromomethyl-4, 6-disubstituted phenol (III), reacting at the temperature of 25-150 ℃ for 2-72 hours, and collecting a ligand compound (I) from a reaction product;
optionally, reacting the benzothiazole ring-substituted aminophenol ligand compound shown in the formula (I) with a zinc metal raw material compound in an organic medium at the reaction temperature of 0-100 ℃ for 2-96 hours, and collecting an aminophenoxy zinc target compound (II) containing the benzothiazole ring from the reaction product;
substituent R in the above preparation method1～R3And X is consistent with the corresponding groups of the amino phenol ligand (I) substituted by the benzothiazole ring and the metal zinc complex (II) thereof;
the zinc metal raw material compound is bis { di (trimethylsilyl) amino } zinc.
The molar ratio of the benzothiazole ring substituted aminophenol ligand compound (I) to the zinc metal raw material compound is 1: 1-1.5; the organic medium is one or two of tetrahydrofuran, diethyl ether, toluene, benzene, petroleum ether and n-hexane.
In the preparation method of the benzothiazole ring substituted aminophenol ligand (I), the synthesis of the 2-chloromethyl benzothiazole can be synthesized according to the following route by a reference method:
wherein, chloroacetyl chloride and anhydrous dichloromethane are mixed and slowly dripped into anhydrous dichloromethane solution of o-aminothiophenol to react in ice-water bath to obtain the target compound (Euro.J.Med.chem.,2011,46, 1706-1712).
In the preparation method of the benzothiazole ring substituted aminophenol ligand (I), 2-bromomethyl-4, 6-disubstituted phenol shown in formula (III) can be synthesized by the method of reference documents according to the following route, wherein the 2, 4-substituted phenol is reacted with paraformaldehyde in acetic acid solution of 33% hydrogen bromide (Inorg. chem.,2002,41, 3656; J.org. chem.,1994,59, 1939):
the zinc complex of the benzothiazole ring substituted aminophenol ligand is a high-efficiency lactone polymerization catalyst, can be used for the polymerization reaction of L-lactide, D-lactide, rac-lactide, meso-lactide, epsilon-caprolactone, β -butyrolactone and α -methyltrimethylene cyclic carbonate, and has the polymerization modes of solution polymerization and melt polymerization.
The benzothiazole ring-substituted aminophenol oxygen radical zinc complex is used as a catalyst to polymerize lactide at the temperature of-40 to 140 ℃, and the preferable temperature is-20 to 110 ℃; the molar ratio of the catalyst to the monomer during polymerization is 1: 1-10000, preferably 1: 100-5000.
The benzothiazole ring substituted aminophenol oxy zinc complex is used as a catalyst, and lactide is reacted in the presence of alcohol at the temperature of-4 DEG CPolymerizing at 0-140 ℃, preferably-20-110 ℃; the molar ratio of the catalyst to the alcohol to the monomer during polymerization is 1: 1-50: 1-10000, preferably 1: 1-50: 100-5000; the alcohol is C1～C10Alkyl alcohols of linear, branched or cyclic structure, C7～C20The mono-or poly-aryl substituted alkyl alcohol of (a).
The benzothiazole ring substituted aminophenol oxygen radical zinc complex is used as a catalyst, and epsilon-caprolactone is polymerized under the condition of adding alcohol or not, wherein the molar ratio of the catalyst to the alcohol to the monomer during polymerization is 1: 0-50: 1-10000, preferably 1: 0-50: 100-5000; the alcohol is C1～C10Alkyl alcohols of linear, branched or cyclic structure, C7～C20The mono-or poly-aryl substituted alkyl alcohol of (a).
The catalyst provided by the invention is convenient to prepare, has stable properties, has higher catalytic activity and high isotactic stereoselectivity, and has wide application prospect. The invention is further illustrated, but not limited, by the following examples.
Detailed Description
Example 1
Synthesis of ligand L1:
(1) synthesis of N- [ (benzothiazol-2-yl) -methyl ] cyclohexylamine
Under the protection of inert gas, cyclohexylamine (24.5mmol,2.43g) and anhydrous K are added into a 100mL three-necked flask2CO3(2.94mmol, 0.41g), a solution of 2-chloromethylbenzothiazole (2.45mmol,0.45g) in 50mL of N, N-dimethylformamide was added dropwise from a constant pressure dropping funnel, followed by reaction for 8 hours. Quenching with water, extracting with dichloromethane, washing with saturated brine, and removing anhydrous MgSO4Drying, filtering, evaporating the solvent under reduced pressure to obtain yellow viscous liquid, and evaporating unreacted cyclohexylamine at 90 deg.C/1 mmHg. The product was analyzed by TLC as the major product spot and used directly in the next reaction, and the yield was about 80% according to nuclear magnetic hydrogen spectroscopy.
(2) Synthesis of ligand L1
Adding N- [ (benzothiazol-2-yl) -methyl into a 100mL single-neck bottle]Cyclohexylamine (5mmol, 1.23g), anhydrous potassium carbonate (5.5mmol, 0.76g) and 50mL of N, N-dimethylformamide were added in portions, 2-bromomethyl-4-methyl-6-tritylphenol (5mmol, 2.22g) was added, reacted at room temperature for 8h, quenched with water, extracted with dichloromethane, washed with saturated brine, anhydrous MgSO 24Drying, evaporation of the solvent under reduced pressure and recrystallization from dichloromethane and petroleum ether gave a white solid (2.5g, 82%).
1H NMR(400MHz,CDCl3,298K):δ9.33(s,1H,OH),7.90(d,3J＝8.0Hz,1H,ArH),7.82(d,3J＝7.4Hz,1H,ArH),7.49–7.42(m,1H,ArH),7.42–7.35(m,1H,ArH),7.24–7.13(m,12H,ArH),7.13–7.06(m,3H,ArH),6.90(d,4J＝1.6Hz,1H,ArH),6.82(d,4J＝1.6Hz,1H,ArH),3.97(s,2H,ArCH2),3.85(s,2H,NCH2C＝N),2.52(m,3J＝12.0,1H,NCH of cyclohexyl),2.17(s,3H,ArCH3),1.85–1.66(m,4H,CH2of cyclohexyl),1.59(s,1H,CH2ofcyclohexyl),1.40–1.19(m,2H,CH2of cyclohexyl),1.17–0.94(m,3H,CH2ofcyclohexyl).13C{1H}NMR(100MHz,CDCl3,298K):δ171.86(SC＝N),153.88,152.95,146.13,135.79,134.06,131.30,131.22,129.46,127.16,127.08,125.89,125.38,124.96,122.82,122.33,121.83(all Ar-C),63.34(Ph3C),59.32(ArCH2),53.59(NCH2C＝N),52.14(NCH),27.95(CH2of cyclohexyl),26.07(CH2of cyclohexyl),25.90(CH2of cyclohexyl),21.04(ArCH3).Anal.Calcd.for C41H40N2OS:C,80.88；H,6.62；N,4.60.Found:C,80.79；H,6.57；4.57％.
Example 2
Synthesis of ligand L2
(1) Synthesis of N- [ (benzothiazol-2-yl) -methyl ] benzylamine
The procedure is as in example 1, except that benzylamine (16.07g,150mmol), potassium carbonate (2.28g,16.5mmol) and 2-chloromethylbenzothiazole (2.75g,15mmol) are used as starting materials. An orange-red oil is obtained.
(2) Synthesis of ligand L2
The procedure was as in example 1(5.50g, 64%) except for using N- [ (benzothiazol-2-yl) -methyl ] benzylamine (14mmol, 3.56g), anhydrous potassium carbonate (15.4mmol, 2.13g) and 2-bromomethyl-4-methyl-6-tritylphenol (14mmol, 6.34g) as starting materials.
1H NMR(400MHz,CDCl3,298K):δ9.49(s,1H,OH),7.97(d,3J＝8.1Hz,1H,ArH),7.85(d,3J＝7.9Hz,1H,ArH),7.54–7.44(m,1H,ArH),7.40(m,3J＝11.2Hz,1H,ArH),7.29–7.17(m,15H,ArH),7.13(t,3J＝6.8Hz,3H,ArH),7.04(m,3J＝14.0,10.5Hz,2H,ArH),6.92(s,1H,ArH),6.84(s,1H,ArH),3.89(s,2H,ArCH2),3.86(s,2H,NCH2C＝N),3.60(s,2H,PhCH2),2.17(s,3H,ArCH3).13C{1H}NMR(100MHz,CDCl3,298K):δ168.20(SC＝N),153.64,152.98,146.12,136.04,135.57,134.16,131.36,131.29,129.99,129.54,128.63,127.74,127.27,127.17,126.10,125.54,125.27,123.14,121.95,121.74(all Ar-C),63.37(Ph3C),58.04(ArCH2),56.97(PhCH2),53.84(NCH2C＝N),21.01(ArCH3).Anal.Calcd.for C42H36N2OS:C,81.78；H,5.88；N,4.54.Found:C,81.80；H,5.86；4.53％.
Example 3
Synthesis of ligand L3
(1) Synthesis of N- [ (benzothiazol-2-yl) -methyl ] N-hexylamine
The procedure is as in example 1, except that n-hexylamine (15.18g,150mmol), potassium carbonate (2.28g,16.5mmol) and 2-chloromethylbenzothiazole (2.75g,15mmol) are used as starting materials. An orange-red oil is obtained.
(2) Synthesis of ligand L3
The procedure was as in example 1(6.30g, 73%) except for using N- [ (benzothiazol-2-yl) -methyl ] N-hexylamine (13.85mmol, 3.44g), anhydrous potassium carbonate (16mmol, 2.21g) and 2-bromomethyl-4-methyl-6-tritylphenol (13.85mmol, 6.14g) as starting materials.
1H NMR(400MHz,CDCl3,298K):δ9.45(s,1H,OH),7.96(d,3J＝7.9Hz,1H,ArH),7.84(d,3J＝7.6Hz,1H,ArH),7.51–7.43(m,1H,ArH),7.40(m,3J＝11.1Hz,1H,ArH),7.24–7.14(m,12H,ArH),7.10(m,3J＝9.2Hz,3H,ArH),6.92(d,4J＝1.6Hz,1H,ArH),6.83(s,1H,ArH),3.91(s,2H,ArCH2),3.84(s,2H,NCH2C＝N),2.49–2.39(m,2H,NCH2CH2),2.18(s,3H,ArCH3),1.50–1.38(m,2H,CH2of n-hexyl),1.17(m,3J＝30.9Hz,6H,CH2of n-hexyl),0.84(q,3J＝7.2Hz,3H,CH2CH3).13C{1H}NMR(101MHz,CDCl3,298K):δ169.11(SC＝N),153.79,152.99,146.13,135.72,134.23,131.29,131.24,129.44,127.28,127.13,126.01,125.46,125.13,122.98,122.16,121.76(all Ar-C),63.34(Ph3C),58.24(ArCH2),54.71(NCH2CH2),53.81(NCH2C＝N),31.67(CH2of n-hexyl),26.97(CH2of n-hexyl),26.26(CH2of n-hexyl),22.62(CH2of n-hexyl),21.03(ArCH3),14.13(CH2CH3).Anal.Calcd.for C41H42N2OS:C,80.62；H,6.93；N,4.59.Found:C,80.73；H,6.79；4.50％.
Example 4
Synthesis of ligand L4
(1) Synthesis of N- [ (benzothiazol-2-yl) -methyl ] cyclopentylamine
The procedure is as in example 1, except that cyclopentylamine (8.52g,100mmol), potassium carbonate (1.52g,11mmol) and 2-chloromethylbenzothiazole (1.84g,10mmol) are used as starting materials. An orange-red oil is obtained.
(2) Synthesis of ligand L4
The procedure was as in example 1(4.90g, 69%) except for using N- [ (benzothiazol-2-yl) -methyl ] cyclopentylamine (12mmol, 2.79g), anhydrous potassium carbonate (13.2mmol, 1.82g) and 2-bromomethyl-4-methyl-6-tritylphenol (12mmol, 5.32g) as starting materials.
1H NMR(400MHz,CDCl3,298K):δ9.53(s,1H,OH),7.94(d,3J＝7.8Hz,1H,ArH),7.87–7.80(m,1H,ArH),7.50–7.42(m,1H,ArH),7.42–7.35(m,1H,ArH),7.25–7.17(m,12H,ArH),7.13(m,3J＝6.6Hz,3H,ArH),6.91(s,1H,ArH),6.86(s,1H,ArH),3.95(s,2H,ArCH2),3.89(s,2H,NCH2C＝N),3.09(m,3J＝8.1Hz,1H,NCH of cyclopentyl),2.18(s,3H,ArCH3),1.82–1.33(m,8H,CH2of cyclopentyl).13C{1H}NMR(100MHz,CDCl3,298K):δ169.95(SC＝N),153.94,152.91,146.13,135.75,134.19,131.28,131.18,129.28,127.25,127.14,125.96,125.44,125.06,122.94,122.28,121.76(all Ar-C),63.37(Ph3C),63.28(ArCH2),55.24(NCH),53.37(NCH2C＝N),28.24(CH2of cyclopentyl),24.02(CH2ofcyclopentyl),21.04(ArCH3).Anal.Calcd.for C40H38N2OS:C,80.77；H,6.44；N,4.71.Found:C,80.74；H,6.36；4.65％.
Example 5
Synthesis of ligand L5
(1) Synthesis of N- [ (benzothiazol-2-yl) -methyl ] cyclooctylamine
The procedure is as in example 1, except that cyclooctylamine (14.54g,114.3mmol), potassium carbonate (1.82g,13.2mmol) and 2-chloromethylbenzothiazole (2.10g,11.43mmol) are used as starting materials. An orange-red oil is obtained.
(2) Synthesis of ligand L5
The procedure was as in example 1(4.10g, 64%) except for using N- [ (benzothiazol-2-yl) -methyl ] cyclooctylamine (10mmol, 2.74g), anhydrous potassium carbonate (11mmol, 1.52g) and 2-bromomethyl-4-methyl-6-tritylphenol (10mmol, 4.43g) as starting materials.
1H NMR(400MHz,CDCl3,298K):δ9.36(s,1H,OH),7.95–7.87(m,1H,ArH),7.82(m,J＝7.9Hz,1H,ArH),7.49–7.43(m,1H,ArH),7.42–7.36(m,1H,ArH),7.25–7.13(m,12H,ArH),7.11–7.05(m,3H,ArH),6.90(d,4J＝1.7Hz,1H,ArH),6.83(d,4J＝1.7Hz,1H,ArH),3.93(s,2H,ArCH2),3.81(s,2H,NCH2C＝N),2.88–2.76(m,1H,NCH of cyclooctyl),2.18(d,J＝5.3Hz,3H,ArCH3),1.86–1.11(m,14H,CH2of cyclooctyl).13C{1H}NMR(101MHz,CDCl3,298K):δ171.88(SC＝N),153.96,152.96,146.13,135.73,133.93,131.28,131.13,129.52,127.13,127.10,125.90,125.39,124.96,122.81,121.93,121.85(all Ar-C),63.33(Ph3C),58.92(ArCH2),53.29(NCH),52.09(NCH2C＝N),29.01(CH2of cyclooctyl),26.40(CH2of cyclooctyl),26.29(CH2of cyclooctyl),25.48(CH2of cyclooctyl),21.01(ArCH3).Anal.Calcd.for C43H44N2OS:C,81.09；H,6.96；N,4.40.Found:C,81.04；H,7.00；4.29％.
Example 6
Synthesis of ligand L6
(1) Synthesis of N- [ (benzothiazol-2-yl) -methyl ] phenethylamine
The procedure is as in example 1, except that phenethylamine (12.12g,100mmol), potassium carbonate (1.52g,11mmol) and 2-chloromethylbenzothiazole (1.84g,10mmol) are used as starting materials. An orange-red oil is obtained.
(2) Synthesis of ligand L6
The procedure of example 1(2.84g, 45%) was followed except for using N- [ (benzothiazol-2-yl) -methyl ] phenethylamine (10mmol, 2.68g), anhydrous potassium carbonate (11mmol, 1.52g) and 2-bromomethyl-4-methyl-6-tritylphenol (10mmol, 4.43g) as starting materials.
1H NMR(400MHz,CDCl3,298K):δ9.25(s,1H,OH),7.96(d,3J＝8.2Hz,1H,ArH),7.83(d,3J＝7.9Hz,1H,ArH),7.47(t,3J＝7.6Hz,1H,ArH),7.39(t,3J＝7.4Hz,1H,ArH),7.24–7.12(m,15H,ArH),7.12–7.06(m,3H,ArH),7.00(d,3J＝7.7Hz,2H,ArH),6.94(s,1H,ArH),6.84(s,1H,ArH),3.97(s,2H,ArCH2),3.90(s,2H,NCH2C＝N),2.72(s,4H,NCH2CH2),2.18(s,3H,ArCH3).13C{1H}NMR(101MHz,CDCl3,298K):δ168.61(SC＝N),153.72,153.00,146.07,139.13,135.69,134.31,131.39,131.24,129.41,128.78,128.53,127.46,127.17,126.34,126.08,125.51,125.21,123.04,122.04,121.78(all Ar-C),63.35(Ph3C),58.28(ArCH2),55.37(NCH2CH2),54.71(NCH2C＝N),33.01(NCH2CH2),21.04(ArCH3).Anal.Calcd.forC43H38N2OS:C,81.87；H,6.07；N,4.44.Found:C,81.49；H,6.06；4.41％.
Example 7
Synthesis of Zinc Complex Zn1
Under the protection of argon, Zn [ N (SiMe) is added3)2]2(1mmol,386mg) was added to a 50mL Schlenk flask and dissolved in 10mL dry toluene, ligand L1(1mmol, 608mg) was slowly added and reacted at room temperature for 8h, the small amount of impurities was removed by filtration and the solvent and free silamine were removed under reduced pressure in vacuo to give a white powdery solid. Toluene and n-hexane were added for recrystallization to obtain a white solid (400mg, 48%).
1H NMR(400MHz,C6D6,298K):δ7.75(d,4J＝8.1Hz,1H,ArH),7.45(d,4J＝7.6Hz,6H,ArH),7.29(d,4J＝2.1Hz,1H,ArH),7.14–7.12(m,2H×0.1,toluene),7.11(m,4J＝8.1Hz,1H,ArH),7.08–7.00(m,3H×0.1,toluene),6.91(m,1H,ArH),6.90(m,3J＝6.6Hz,7H,ArH),6.70(d,4J＝2.1Hz,1H,ArH),6.60(t,4J＝7.6Hz,3H,ArH),4.47(d,2J＝12.0Hz,1H,ArCH2),3.75(d,2J＝17.5Hz,1H,NCH2C＝N),3.13(d,2J＝17.5Hz,1H,NCH2C＝N),3.09(d,2J＝12.0Hz,1H,ArCH2),2.88(d,1H,CH2of cyclohexyl),2.51(m,1H,NCH of cyclohexyl),2.24(s,3H,ArCH3),2.11(s,3H×0.1,toluene),1.63(d,2H,CH2of cyclohexyl),1.52–1.34(m,2H,CH2of cyclohexyl),1.26(m,1H,CH2of cyclohexyl),1.17–0.97(m,2H,CH2of cyclohexyl),0.98–0.69(m,2H,CH2of cyclohexyl),0.20(s,18H,N(Si(CH3)3)2).13C{1H}NMR(100MHz,C6D6,298K):δ173.87(SC＝N),164.59,148.42,147.92,137.90(toluene),137.53,133.84,133.12,131.98,131.72,129.34(toluene),128.57(toluene),127.16,126.99,126.53,125.70(toluene),125.00,124.40,121.53,120.97,120.51(all Ar-C),64.11(Ph3C),63.84(ArCH2),54.01(NCH2C＝N),49.30(NCH),30.72(CH2of cyclohexyl),26.71(CH2of cyclohexyl),26.05(CH2of cyclohexyl),25.96(CH2of cyclohexyl),23.82(CH2of cyclohexyl),21.45(ArCH3),21.04(toluene),6.01(N(Si(CH3)3)2).Anal.Calcd.for C47H57N3OSSi2Zn·0.1C7H8:C,67.72；H,6.89；N,5.04.Found:C,67.98；H,6.91；N,4.99％.
Example 8
Synthesis of Zinc Complex Zn2
Under the protection of argon, Zn [ N (SiMe) is added3)2]2(1mmol,386mg) was added to a 50mL Schlenk flask, dissolved in 10mL anhydrous tetrahydrofuran, ligand L2(1mmol, 617mg) was slowly added, reacted at room temperature for 8h, filtered to remove a small amount of impurities, and the solvent and free silamine were removed under reduced pressure in vacuo to give a red foamy solid. Tetrahydrofuran and n-hexane were added to the solution to recrystallize, giving a pale red solid (429mg, 51%).
1H NMR(400MHz,C6D6,298K):δ7.71(d,3J＝8.2Hz,1H,ArH),7.45(d,3J＝7.7Hz,6H,ArH),7.27(d,4J＝1.8Hz,1H,ArH),7.10(m,3J＝8.2Hz,5H,ArH),6.91(m,3J＝7.7Hz,7H,ArH),6.85–6.78(m,2H,ArH),6.61(m,3J＝7.3Hz,3H,ArH),6.42(d,4J＝1.8Hz,1H,ArH),4.54(d,2J＝12.2Hz,1H,ArCH2),4.21(d,2J＝14.2Hz,1H,PhCH2),3.90(d,2J＝14.2Hz,1H,PhCH2),3.58(t,4H×0.5,THF),3.50(d,2J＝17.5Hz,1H,NCH2C＝N),3.38(d,2J＝12.2Hz,1H,ArCH2),3.27(d,2J＝17.5Hz,1H,NCH2C＝N),2.09(s,3H,ArCH3),1.47–1.37(m,4H×0.5,THF),0.26(s,18H,N(Si(CH3)3)2).13C{1H}NMR(100MHz,C6D6,298K):δ173.27(SC＝N),164.71,148.46,147.92,137.91,133.76,133.32,132.14,131.72,131.23,128.99,128.94,127.33,126.98,126.64,125.00,124.26,121.65,120.50,120.20(all Ar-C),64.14(Ph3C),59.63(ArCH2),59.08(PhCH2),48.18(NCH2C＝N),20.86(ArCH3),6.41(N(Si(CH3)3)2).Anal.Calcd.for C48H53N3OSSi2Zn·0.5C4H8O:C,68.52；H,6.47；N,4.68.Found:C,68.43；H,6.55；N,4.79％.
Example 9
Synthesis of Zinc Complex Zn3
Under the protection of argon, Zn [ N (SiMe) is added3)2]2(1mmol,386mg) was added to a 50mL Schlenk flask and dissolved in 10mL anhydrous tetrahydrofuran, ligand L3(1mmol, 611mg) was slowly added and reacted at room temperature for 8h, a small amount of impurities was removed by filtration and the solvent and free silamine were removed under reduced pressure in vacuo to give a yellow foamy solid. Tetrahydrofuran and n-hexane were added to the solution to recrystallize the solution, yielding a pale yellow solid (393mg, 47%).
1H NMR(400MHz,C6D6,298K):δ7.74(d,3J＝8.2Hz,1H,ArH),7.43(d,3J＝7.5Hz,6H,ArH),7.31(d,4J＝2.2Hz,1H,ArH),7.12–7.03(m,2H,ArH),6.94–6.83(m,7H,ArH),6.69(d,4J＝2.2Hz,1H,ArH),6.55(t,3J＝7.3Hz,3H,ArH),4.66(d,2J＝12.2Hz,1H,ArCH2),3.86(d,2J＝17.3Hz,1H,NCH2C＝N),2.84(d,2J＝12.2Hz,1H,ArCH2),2.71(m,1H,CH2of n-hexyl),2.57(d,2J＝17.3Hz,1H,NCH2C＝N),2.24(s,3H,ArCH3),2.06(m,2H,CH2of n-hexyl),1.45(m,1H,CH2of n-hexyl),1.33–1.10(m,5H,CH2of n-hexyl),0.98(m,1H,CH2of n-hexyl),0.89(t,3J＝6.8Hz,3H,CH2CH3),0.18(s,18H,N(Si(CH3)3)2).13C{1H}NMR(100MHz,C6D6,298K):δ172.09(SC＝N),163.18,147.39,146.88,137.05,132.81,132.27,131.01,130.73,126.14,125.96,125.66,124.00,123.52,120.54,119.82,119.51(all Ar-C),63.11(Ph3C),59.13(ArCH2),59.04(NCH2CH2),52.31(NCH2C＝N),30.91(CH2of n-hexyl),26.51(CH2of n-hexyl),23.92(CH2of n-hexyl),22.10(CH2of n-hexyl),20.07(ArCH3),13.25(CH2CH3),5.08(N(Si(CH3)3)2).Anal.Calcd.for:C47H59N3OSSi2Zn:C,67.56；H,7.12；N,5.03.Found:C,67.43；H,7.18；N,5.03％.
Example 10
Synthesis of Zinc Complex Zn4
Under the protection of argon, Zn [ N (SiMe) is added3)2]2(1mmol,386mg) was added to a 50mL Schlenk flask, dissolved in 10mL anhydrous tetrahydrofuran, ligand L4(1mmol, 595mg) was slowly added, reacted at room temperature for 8h, filtered to remove a small amount of impurities, and the solvent and free silamine were removed under reduced pressure in vacuo to give a yellow foamy solid. Tetrahydrofuran and n-hexane were added for recrystallization to give a pale yellow solid (459mg, 56%).
1H NMR(400MHz,C6D6,298K):δ7.72(d,3J＝8.1Hz,1H,ArH),7.44(d,3J＝7.4Hz,6H,ArH),7.30(d,4J＝2.0Hz,1H,ArH),7.11(m,1H,ArH),7.06(d,3J＝8.1Hz,1H,ArH),6.90(m,7H,ArH),6.69(d,4J＝2.0Hz,1H,ArH),6.58(t,3J＝7.4Hz,3H,ArH),4.58(d,2J＝12.0Hz,1H,ArCH2),3.78(d,2J＝17.5Hz,1H,NCH2C＝N),3.58(t,4H×0.6,THF),3.07(m,1H,NCH),3.02(d,2J＝12.0Hz,1H,ArCH2),2.83(d,2J＝17.5Hz,1H,NCH2C＝N),2.24(s,3H,ArCH3),1.99(m,1H,CH2of cyclopentyl),1.80–1.65(m,1H,CH2of cyclopentyl),1.35(m,8.4H,6H of cyclopentyl and 4H×0.6,THF),0.21(s,18H,N(Si(CH3)3)2).13C{1H}NMR(100MHz,C6D6,298K):δ173.83(SC＝N),164.50,148.39,147.91,137.66,133.79,133.16,132.02,131.70,127.12,126.97,126.56,124.98,124.47,121.52,120.64,120.39(All Ar-C),67.83(THF),67.35(ArCH2),64.08(Ph3C),55.52(NCH),51.57(NCH2C＝N),29.75(CH2ofcyclopentyl),25.82(THF),24.80(CH2of cyclopentyl),24.21(CH2of cyclopentyl),23.92(CH2of cyclopentyl),21.02(ArCH3),6.20(N(Si(CH3)3)2).Anal.Calcd.for:C46H55N3OSSi2Zn·0.6C4H8O:C,67.37；H,6.99；N,4.87.Found:C,67.14；H,6.94；N,5.12％.
Example 11
Synthesis of Zinc Complex Zn5
Under the protection of argon, Zn [ N (SiMe) is added3)2]2(1mmol,386mg) was added to a 50mL Schlenk flask, dissolved in 10mL anhydrous tetrahydrofuran, ligand L5(1mmol, 637mg) was slowly added, reacted at room temperature for 8h, filtered to remove a small amount of impurities, and the solvent and free silamine were removed under reduced pressure in vacuo to give a yellow foamy solid. Tetrahydrofuran and n-hexane were added to the solution to recrystallize the solution, yielding a pale yellow solid (440mg, 51%).
1H NMR(400MHz,C6D6,298K):δ7.77(d,3J＝8.2Hz,1H,ArH),7.45(d,3J＝7.4Hz,6H,ArH),7.31(d,4J＝2.2Hz,1H,ArH),7.14–7.08(m,2.1H,1H of ArH and 2H×0.55,toluene),7.08–6.99(m,2.65H,1H of ArH and 3H×0.55,toluene),6.95–6.85(m,7H,ArH),6.71(d,4J＝2.2Hz,1H,ArH),6.58(t,3J＝7.4Hz,3H,ArH),4.54(d,2J＝12.0Hz,1H,ArCH2),3.56(d,2J＝17.4Hz,1H,NCH2C＝N),3.03(d,2J＝12.0Hz,1H,ArCH2),2.84(d,2H,1Hof NCH2C＝N and 1H of NCH),2.77–2.65(m,1H,CH2of cyclooctyl),2.27(s,3H,ArCH3),2.11(s,3H×0.55,toluene),1.72–1.11(m,12H,CH2of cyclooctyl),1.12–0.97(m,1H,CH2of cyclooctyl),0.21(s,18H,N(Si(CH3)3)2).13C{1H}NMR(100MHz,C6D6,298K):δ173.90(SC＝N),164.59,148.58,147.93,137.89(toluene),137.43,133.78,133.10,131.91,131.72,129.34(toluene),128.57(toluene),127.12,126.99,126.49,125.70(toluene),124.98,124.44,121.58,120.88,120.39(All Ar-C),64.08(ArCH2),63.63(Ph3C),53.93(NCH),49.73(NCH2C＝N),33.15(CH2of cyclooctyl),29.15(CH2of cyclooctyl),27.65(CH2ofcyclooctyl),26.80(CH2of cyclooctyl),26.39(CH2of cyclooctyl),24.05(CH2ofcyclooctyl),23.88(CH2of cyclooctyl),21.08(toluene),21.05(ArCH3),6.04(N(Si(CH3)3)2).Anal.Calcd.for:C49H61N3OSSi2Zn·0.55C7H8:C,69.58；H,7.23；N,4.61.Found:C,69.64；H,7.11；N,4.59％.
Example 12
Synthesis of Zinc Complex Zn6
Under the protection of argon, Zn [ N (SiMe) is added3)2]2(1mmol,386mg) was added to a 50mL Schlenk flask and dissolved in 10mL dry toluene, ligand L6(1mmol, 631mg) was slowly added and reacted at room temperature for 8h, the small amount of impurities was removed by filtration and the solvent and free silamine were removed under reduced pressure in vacuo to give a yellow foamy solid. Toluene and n-hexane were added for recrystallization to give a pale yellow solid (445mg, 52%).
1H NMR(400MHz,C6D6,298K):δ7.73(d,3J＝8.1Hz,1H,ArH),7.44(d,3J＝7.4Hz,6H,ArH),7.32(d,4J＝2.2Hz,1H,ArH),7.15–6.99(m,12H,7H of ArH and 5H×1,toluene),6.95–6.84(m,7H,ArH),6.69(d,4J＝2.2Hz,1H,ArH),6.58(t,3J＝7.3Hz,3H,ArH),4.76(d,2J＝12.1Hz,1H,ArCH2),3.87(d,2J＝17.3Hz,2H,NCH2C＝N),3.30(m,1H,NCH2CH2),3.10(td,2J＝12.2,3J＝5.0Hz,1H,NCH2CH2),2.95(d,2J＝12.1Hz,1H,ArCH2),2.86(m,1H,NCH2CH2),2.64(d,2J＝17.3Hz,1H,NCH2C＝N),2.42(td,2J＝12.0,3J＝5.0Hz,1H,NCH2CH2),2.24(s,3H,ArCH3),2.11(s,3H×1,toluene),0.18(s,18H,N(Si(CH3)3)2).13C{1H}NMR(100MHz,C6D6,298K):δ173.01,164.16,148.35,147.85,138.64,138.05,137.89(toluene),133.87,133.25,132.02,131.71,129.33(toluene),129.01,128.88,128.57(toluene),127.17,126.97,126.67,125.70(toluene),125.01,124.47,121.55,120.65,120.61(All Ar-C),64.10(Ph3C),61.05(ArCH2),60.32(NCH2CH2),53.02(NCH2C＝N),31.08(PhCH2),21.46(ArCH3),21.04(toluene),6.16(N(Si(CH3)3)2).Anal.Calcd.for:C49H55N3OSSi2Zn·1C7H8:C,70.97；H,6.70；N,4.43.Found:C,71.13；H,6.31；N,4.43％.
Example 13
Racemic lactide (0.144g,1.0mmol) was added to a polymerization flask under argon and dissolved in 0.5mL of toluene. 0.5mL of a toluene solution of catalyst Zn1 was measured and added to the polymerization flask. [ rac-LA]0＝1.0M，[Zn]0＝0.002M，[Zn]0:[rac-LA]01: 500. Controlling the reaction temperature to be 25 +/-1 ℃, reacting for 5.5 hours, and adding petroleum ether to terminate the reaction. The solvent was removed by suction, the residue was dissolved in methylene chloride, and methanol was added to precipitate the polymer. Vacuum drying for 24 h. Conversion rate: 89%, Mn＝10.5×104g/mol, molecular weight distribution PDI of 1.35, isotacticity Pm＝0.91。
Example 14
The procedure of example 13 was repeated except that the solvent was replaced with tetrahydrofuran, and after 3.5 hours, the conversion: 93%, Mn＝12.3×104g/mol, molecular weight distribution PDI of 1.49, isotacticity Pm＝0.86。
Example 15
The procedure of example 13 was followed, except that the catalyst was replaced with Zn2, and after 5 hours, the conversion: 91%, Mn＝12.0×104g/mol, molecular weight distribution PDI of 1.49, isotacticity Pm＝0.87。
Example 16
The same procedure as in example 13 was repeated except that the catalyst was changed to Zn2 and the solvent was changed to tetrahydrofuran, and the conversion after 2.5 hours: 90%, Mn＝13.4×104g/mol, molecular weight distribution PDI of 1.48, isotacticity Pm＝0.86。
Example 17
The procedure of example 13 was repeated except that the catalyst was changed to Zn3, and the conversion rate after 4.5 hours: 93%, Mn＝40.5×104g/mol, molecular weight distribution PDI of 1.30, isotacticity Pm＝0.89。
Example 18
The procedure of example 13 was repeated except that the catalyst was replaced with Zn3 and the solvent was replaced with tetrahydrofuran, and the conversion after 2 hours: 92%, Mn＝12.1×104g/mol, molecular weight distribution PDI of 1.50, isotacticity Pm＝0.85。
Example 19
The procedure of example 13 was repeated except that the catalyst was changed to Zn4, and after 7.5 hours, the conversion: 88%, Mn＝33.4×104g/mol, molecular weight distribution PDI of 1.32, isotacticity Pm＝0.89。
Example 20
The procedure of example 13 was repeated except that the catalyst was changed to Zn5, and after 7 hours, the conversion: 95%, Mn＝20.0×104g/mol, molecular weight distribution PDI 1.45, degree of isotacticity Pm＝0.90。
Example 21
The procedure of example 13 was repeated except that the catalyst was replaced with Zn5 and the solvent was replaced with tetrahydrofuran, and the conversion after 5 hours: 91%, Mn＝16.3×104g/mol, molecular weight distribution PDI of 1.45, isotacticity Pm＝0.87。
Example 22
The procedure of example 13 was followed, except that the catalyst was replaced with Zn6, and after 2 hours, the conversion: 91%, Mn＝14.0×104g/mol, molecular weight distribution PDI of 1.28, isotacticity Pm＝0.88。
Example 23
The same procedure as in example 13 was repeated except that the catalyst was changed to Zn6 and the solvent was changed to tetrahydrofuran, and the conversion after 2.75 hours: 90%, Mn＝19.2×104g/mol, molecular weight distribution PDI of 1.39, isotacticity Pm＝0.85。
Example 24
Racemic lactide (0.144g,1.0mmol) was added to a polymerization flask under argon and dissolved with 0.5mL of isopropanol in toluene. 0.5mL of a toluene solution of catalyst Zn1 was measured and added to the polymerization flask. [ rac-LA]0＝1.0M，[Zn]0＝0.002M，[Zn]0:[iPrOH]0:[rac-LA]01:1: 500. Controlling the reaction temperature to be 25 +/-1 ℃, reacting for 1.2 hours, and adding petroleum ether to terminate the reaction. The solvent was removed by suction, the residue was dissolved in methylene chloride, and methanol was added to precipitate the polymer. Vacuum drying for 24 h. Conversion rate: 90%, Mn＝9.8×104g/mol, molecular weight distribution PDI of 1.25, isotacticity Pm＝0.89。
Example 25
The procedure of example 24 was repeated except that the solvent was replaced with tetrahydrofuran, and after 1.7 hours, the conversion: 90%, Mn＝6.5×104g/mol, molecular weight distribution PDI of 1.32, isotacticity Pm＝0.84。
Example 26
By removing catalyst by exchanging for Zn2, the same procedure as in example 24 was repeated except that, after 1 hour of reaction, the conversion: 90%, Mn＝11×104g/mol, molecular weight distribution PDI of 1.24, isotacticity Pm＝0.87。
Example 27
The same procedure as in example 24 was repeated except that the catalyst was changed to Zn2 and the solvent was changed to tetrahydrofuran, and the conversion after 1.3 hours: 91%, Mn＝7.0×104g/mol, molecular weight distribution PDI of 1.27, isotacticity Pm＝0.86。
Example 28
The same procedure as in example 24 was carried out except that the catalyst was changed to Zn3, and after 1 hour of reaction, the conversion: 94%, Mn＝12.8×104g/mol, molecular weight distribution PDI of 1.28, isotacticity Pm＝0.89。
Example 29
The procedure of example 24 was repeated except that the catalyst was changed to Zn4, and after 2.5 hours, the conversion: 93%, Mn＝10.7×104g/mol, molecular weight distribution PDI of 1.31, isotacticity Pm＝0.85。
Example 30
The same procedure as in example 24 was carried out, except that the catalyst was changed to Zn5, and the conversion rate after 1.5 hours: 87%, Mn＝9.6×104g/mol, molecular weight distribution PDI of 1.20, isotacticity Pm＝0.87。
Example 31
The same procedure as in example 24 was repeated except that the catalyst was changed to Zn5 and the solvent was changed to tetrahydrofuran, and the conversion after 2.5 hours: 91%, Mn＝7.6×104g/mol, molecular weight distribution PDI of 1.23, isotacticity Pm＝0.85。
Example 32
The same procedure as in example 24 was carried out, except that the catalyst was changed to Zn6, and after 1.75 hours, the conversion: 88%, Mn＝8.6×104g/mol, molecular weight distribution PDI of 1.09, isotacticity Pm＝0.85。
Example 33
Catalyst removal and replacementTo Zn6, the solvent was replaced with tetrahydrofuran, and the same procedures as in EXAMPLE 24 were carried out, after 2.25 hours, the conversion was: 90%, Mn＝7.1×104g/mol, molecular weight distribution PDI of 1.16, isotacticity Pm＝0.84。
Example 34
The same procedure as in example 24 was carried out, except that the polymerization temperature was 0 ℃, and that after 11 hours, the conversion: 90%, Mn＝10.4×104g/mol, molecular weight distribution PDI of 1.07, isotacticity Pm＝0.89。
Example 35
The procedure of EXAMPLE 24 was carried out except that the polymerization temperature was changed to-20 ℃ and, after 72 hours of reaction, the conversion: 52%, Mn＝7.7×104g/mol, molecular weight distribution PDI of 1.28, isotacticity Pm＝0.93。
Example 36
To a 10mL polymerization flask was added racemic lactide (144mg, 1.00mmol), 0.1mL of isopropanol/toluene solution was added, and 0.1mL of a toluene solution of catalyst Zn1 was added. Maintenance of [ rac-LA]0/[Zn]0/[iPrOH]1000:1: 1. Placing in oil bath at 110 + -1 deg.C, stirring, reacting for 5min, and adding petroleum ether to terminate polymerization. The solvent was removed by suction, the residue was dissolved in methylene chloride, and methanol was added to precipitate the polymer. Vacuum drying for 24 h. Conversion rate: 83%, Mn＝25.0×104g/mol, molecular weight distribution PDI of 1.47, isotacticity Pm＝0.76。
Example 37
Except for [ rac-LA]0/[Zn]0/[iPrOH]The procedure was as in example 36 except 1000:1: 5. After 3min of reaction, conversion: 89%, Mn＝6.4×104g/mol, molecular weight distribution PDI of 1.46, isotacticity Pm＝0.72。
Example 38
Except for [ rac-LA]0/[Zn]0/[iPrOH]The procedure was as in example 36 except that the ratio was 2000:1: 10. After 5min of reaction, conversion: 93%, Mn＝6.8×104g/mol, molecular weight distribution PDI of 1.48, isotacticity Pm＝0.66。
Example 39
Except for [ rac-LA]0/[Zn]0/[iPrOH]The procedure was as in example 36 except that the ratio was 5000:1: 50. After 10min of reaction, conversion: 86%, Mn＝5.8×104g/mol, molecular weight distribution PDI of 1.18, isotacticity Pm＝0.66。
Example 40
The same procedure as in example 24 was repeated except that the solvent was replaced with tetrahydrofuran and the monomer was replaced with D-LA, and 80min later, the conversion was: 92%, Mn＝7.5×104g/mol, molecular weight distribution PDI 1.30.
EXAMPLE 41
The same procedure as in example 24 was repeated except that the solvent was replaced with tetrahydrofuran and the monomer for polymerization was replaced with L-LA, and the reaction time was 80min, the conversion: 88%, Mn＝7.0×104g/mol, molecular weight distribution PDI 1.33.
Example 42
The procedure of EXAMPLE 24 was followed except that the polymerized monomers were changed to epsilon-caprolactone, and after 25min, the conversion was: 91%, Mn＝5.10×104g/mol, molecular weight distribution PDI 1.24.
Claims (10)
1. A benzothiazole ring substituted aminophenol ligand (I) and its metallic zinc complex (II) characterized by the following general formula:
in the formulae (I), (II):
R1～R2each represents hydrogen, C1～C20Alkyl of linear, branched or cyclic structure, C7～C30Mono-or poly-aryl-substituted alkyl of (a), halogen;
R3represents C1～C20Alkyl of linear, branched or cyclic structure, C7～C30Mono-or polyaryl-substituted alkyl of, C6～C18Aryl of (a);
x represents an amino group NR4R5Wherein R is4～R5Are respectively C1～C6Alkyl of linear, branched or cyclic structure, trimethylsilyl, triethylsilyl, dimethylhydrosilyl, R4And R5May be the same or different.
2. Benzothiazole ring-substituted aminophenol ligands (I) and their metallic zinc complexes (II) according to claim 1, characterized in that R1～R2Is hydrogen, C1～C8Alkyl of linear, branched or cyclic structure, C7～C20Mono-or poly-aryl-substituted alkyl of (a), halogen; r3Is C1～C8Alkyl of linear, branched or cyclic structure, C7～C20Mono-or polyaryl-substituted alkyl of, C6～C12Aryl of (a); x is di (trimethyl silicon) amino, di (triethyl silicon) amino or di (dimethyl hydrogen silicon) amino.
3. Benzothiazole ring-substituted aminophenol ligands (I) and their metallic zinc complexes (II) according to claim 1, characterized in that R1～R2Is hydrogen, methyl, tert-butyl, cumyl, trityl or halogen; r3Is methyl, ethyl, isopropyl, n-butyl, tert-butyl, n-hexyl, cyclopentyl, cyclohexyl, n-octyl, cyclooctyl, benzyl or phenethyl; x is di (trimethyl silicane) amino.
4. A process for preparing a benzothiazole ring-substituted aminophenol ligand (I) and its metal zinc complex (II) according to any one of claims 1 to 3, comprising the steps of:
reacting 2-chloromethylbenzothiazole with primary amine to generate corresponding secondary amine, adding 2-bromomethyl-4, 6-disubstituted phenol (III), reacting at the temperature of 25-150 ℃ for 2-72 hours, and collecting a ligand compound (I) from a reaction product;
optionally, reacting the benzothiazole ring-substituted aminophenol ligand compound shown in the formula (I) with a zinc metal raw material compound in an organic medium at the reaction temperature of 0-100 ℃ for 2-96 hours, and collecting a benzothiazole ring-substituted aminophenoxy zinc target compound (II) from a reaction product;
substituent R in the above preparation method1～R3Corresponding groups of the benzothiazole ring-substituted aminophenol ligand (I) and the metal zinc complex thereof (II) according to any one of claims 1 to 3;
the zinc metal raw material compound has a general formula of ZnX2And X is identical with the corresponding group of the benzothiazole ring-substituted aminophenoxy zinc complex (II) according to any one of claims 1 to 3.
5. The method according to claim 4, wherein the zinc metal raw material compound is bis { di (trimethylsilyl) amino } zinc, and the molar ratio of the benzothiazole ring-substituted aminophenol ligand compound to the zinc metal raw material compound is 1:1 to 1.5; the organic medium is one or two of tetrahydrofuran, diethyl ether, toluene, benzene, petroleum ether and n-hexane.
6. Use of a benzothiazole ring-substituted aminophenoxy zinc complex according to any one of claims 1 to 3 in the ring-opening polymerization of lactones.
7. Use according to claim 6, characterized in that the lactone is selected from the group consisting of L-lactide, D-lactide, rac-lactide, meso-lactide, epsilon-caprolactone, β -butyrolactone, α -methyltrimethylene cyclic carbonate.
8. Use according to claim 6, wherein lactide is polymerized using the benzothiazole ring-substituted aminophenoxy zinc complex of any one of claims 1 to 3 as a catalyst, and the molar ratio of the catalyst to the monomer in the polymerization is 1:1 to 10000.
9. The use according to claim 6, wherein the benzothiazole ring-substituted amino phenol oxy zinc complex of any one of claims 1 to 3 is used as a catalyst to polymerize lactide in the presence of alcohol, wherein the molar ratio of the catalyst to the alcohol and the monomer is 1:1 to 50:1 to 10000; the alcohol is C1～C10Alkyl alcohols of linear, branched or cyclic structure, C7～C20The mono-or poly-aryl substituted alkyl alcohol of (a).
10. The use according to claim 6, wherein the benzothiazole ring-substituted aminophenoxy zinc complex of any one of claims 1 to 3 is used as a catalyst to polymerize epsilon-caprolactone with or without the addition of alcohol; the alcohol is C1～C10Alkyl alcohols of linear, branched or cyclic structure, C7～C20The mono-or poly-aryl substituted alkyl alcohol of (a).
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