CN108239017A - Ligand of the aldehyde radical containing bigcatkin willow and its preparation method and application - Google Patents
Ligand of the aldehyde radical containing bigcatkin willow and its preparation method and application Download PDFInfo
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- CN108239017A CN108239017A CN201711315695.2A CN201711315695A CN108239017A CN 108239017 A CN108239017 A CN 108239017A CN 201711315695 A CN201711315695 A CN 201711315695A CN 108239017 A CN108239017 A CN 108239017A
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- 239000003446 ligand Substances 0.000 title claims abstract description 137
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 240000000203 Salix gracilistyla Species 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 156
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 55
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 54
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 cyclic lactone Chemical group 0.000 claims abstract description 23
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 28
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 25
- 229910052794 bromium Chemical group 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 18
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 10
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 74
- 238000005406 washing Methods 0.000 description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 238000001035 drying Methods 0.000 description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 25
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 239000011261 inert gas Substances 0.000 description 22
- 235000019445 benzyl alcohol Nutrition 0.000 description 20
- 239000003708 ampul Substances 0.000 description 19
- 150000003938 benzyl alcohols Chemical class 0.000 description 19
- 229910001873 dinitrogen Inorganic materials 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 238000012869 ethanol precipitation Methods 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 229920000747 poly(lactic acid) Polymers 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000003808 methanol extraction Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 125000001246 bromo group Chemical group Br* 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 150000003613 toluenes Chemical class 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 229920000954 Polyglycolide Polymers 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ROFVXGGUISEHAM-UHFFFAOYSA-N URB597 Chemical compound NC(=O)C1=CC=CC(C=2C=C(OC(=O)NC3CCCCC3)C=CC=2)=C1 ROFVXGGUISEHAM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- TUCIOBMMDDOEMM-RIYZIHGNSA-N tyrphostin B42 Chemical compound C1=C(O)C(O)=CC=C1\C=C(/C#N)C(=O)NCC1=CC=CC=C1 TUCIOBMMDDOEMM-RIYZIHGNSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Ligand the invention discloses a kind of aldehyde radical containing bigcatkin willow and its preparation method and application.Ligand of the present invention can be complexed to form complex with trimethyl aluminium with N, N, O, O quad-tree index.Ligand structure of the present invention is special, preparation method is simple, the aluminum complex of formation can be as the catalyst of cyclic lactone ring-opening polymerization, the catalyst activity is high, and stereoselectivity is high, and reaction rate is quickly, polymerisation is easy to operate, and the product of different molecular weight can be controllably obtained, selectivity is wide, there is good market prospects.
Description
Technical field
The present invention relates to asymmetric nitrogen oxygen ligands of a kind of divalent and its preparation method and application, and in particular to one kind contains bigcatkin willow
The application of the ligand of ligand of aldehyde radical and preparation method thereof and the catalyst of ring-opening polymerisation as cyclic lactone.
Background technology
Conventional plastic using oil as raw material has very big influence in the industry since the forties in last century, these biographies
System plastics have a unrivaled advantage, but there are two it is fatal the shortcomings that：Non-renewable and non-biodegradable.In oil as not
In the case that renewable resource faces exhaustion, the fast development of high molecule plastic material of petroleum is relied on by very big system
About, and high molecular polymerization plastic material is difficult to degrade, and a large amount of high molecular polymerization plastic material waste accumulates in existing for a long time
Grow directly from seeds and pollute also gradually exacerbation in living caused by environment for human survival.Find the renewable resource instead of oil, development environment
Friendly, biodegradation type new material become the trend of following high molecular polymerization plastic material development.
High molecular material of the polyester for the environmental type of biodegradable, the substitute as oil product are more next
More it is concerned by people.In natural living environment, discarded polylactone material can thoroughly be divided by the microorganism in soil
Xie Chengshui and carbon dioxide, it is environmentally friendly and renewable.Because polyester is nontoxic, nonirritant, and has good biocompatibility,
It is therefore widely used in medicine and field of environment protection, such as operation suture thread, packaging, drug controlled release and tissue engineering bracket
Deng.The performance that the excellent biocompatibility of polylactone, biological degradability and sustainable development utilize, makes it have become 21 generation
The most promising high molecular material of discipline.
The advantages of easily method of synthesizing polyester is the ring-opening polymerisation method of cyclic lactone, this synthetic method be：Polymerization
Controllability, relatively narrow molecular weight distribution.Currently used catalyst is mostly the complex that ligand and metal are formed, in catalyst
Metal includes magnesium, calcium, germanium, tin, aluminium, zinc, iron, titanium, zirconium, group of the lanthanides etc..In addition to metal, the selection of ligand is for ring-opening polymerization
Speed, the performance of products obtained therefrom it is all very crucial, in the case of same metal, often ligand replacement and selection can show
Go out unexpected catalytic effect, therefore it is most important to study the good ligand of performance.
Invention content
The present invention provides the ligands of two kinds of aldehyde radicals containing bigcatkin willow, and the ligand structure is special, have nitrogen, oxygen quad-tree index, energy
Complex is formed with aluminium methyl, which can be as the catalyst of cyclic lactone ring-opening polymerization, and catalytic activity is high, three-dimensional
High selectivity, performance are good.
The present invention also provides the preparation method of the ligand of the aldehyde radical containing bigcatkin willow, this method prepares simple, it is easy to accomplish.
The present invention also provides ligand of the ligand as the catalyst of cyclic lactone ring-opening polymerization of the aldehyde radical containing bigcatkin willow
Application and the ligand made of cyclic lactone ring-opening polymerization catalyst.
The present invention is in the young project of National Nature fund committee（No 21104026）Subsidy under complete, skill of the present invention
Art scheme is as follows：
The present invention provides the ligand of two kinds of aldehyde radicals containing bigcatkin willow, one of which has following structural formula shown in formula A, the ligand
It can be referred to as compound A or ligand A：
；
Second of ligand has the structural formula as shown in following formula II, which can be referred to as ligand II or compound ii：
。
The present invention has obtained the ligand of above two special construction by research, containing bigcatkin willow aldehyde radical in the ligand, is based on
The special selection of the ligand structure, the aluminium haveing excellent performance that catalysis cyclic lactone ring-opening polymerization can be formed with metallic aluminium are matched
Close object.Substituent group selects to have catalytic performance of the aluminum complex as cyclic lactone ring-opening polymerization catalyst in ligand
Larger impact.Wherein, R is the alkane or halogen of hydrogen, C1-C4, and the halogen is fluorine, chlorine, bromine or iodine.Further, R is tertiary fourth
Stereoselectivity is best during base, and catalytic activity is best when R is bromine.
The present invention provides the preparation method of the ligand of above two aldehyde radical containing bigcatkin willow, wherein, the system of ligand A shown in formula A
Preparation Method includes the following steps：P-methyl benzenesulfonic acid is dissolved into dimethylbenzene, is first slowly added into p-methyl benzenesulfonic acid equimolar amounts
Ethylenediamine adds the phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, and then heating carries out back flow reaction, after reaction
It is cooled to room temperature, filters to take solid, obtained solid is dissolved into dichloromethane, it is molten that saturated sodium bicarbonate water is then slowly added dropwise
Liquid is reacted, and to slough p-methyl benzenesulfonic acid, liquid separation after reaction is dried gained organic phase with anhydrous magnesium sulfate, then
Solvent is spin-dried for, obtains the ethylenediamine of unilateral phthalic anhydride protection；
The ethylenediamine that unilateral phthalic anhydride is protected and the salicylide of equimolar amounts or derivatives thereof dissolve in methyl alcohol, add
Heat carries out back flow reaction, cools down, filters after reaction, obtained solid is washed with cold methanol, dried, and obtains ligand shown in formula A；Institute
The structural formula of salicylaldehyde derivatives is stated as shown in following formula B, wherein R be hydrogen, C1-C4 alkane or halogen, preferably tertiary butyl or
Bromine；
。
The preparation method of ligand includes the following steps shown in formula II：Ligand shown in formula A is added in organic solvent, -10
~0 oTrimethyl aluminium is added under C, reaction temperature is made to be warmed to room temperature naturally after adding, temperature is then risen to 30~110oC is carried out
Reaction, adds in water into reaction solution after reaction, and liquid separation is stood after being sufficiently mixed, and collects organic phase obtained by liquid separation, and recycling has
Solvent obtains crude product, and crude product is recrystallized, and obtains ligand shown in formula II.
Above-mentioned II preparation method reaction equation of ligand is as follows, and ligand A first reacts to form aluminum complex with trimethyl aluminium, gained aluminium
Complex is broken water sensitive, in the presence of water Al-O keys, is hydrolyzed into ligand II and Al (OH)3, ligand II enters organic
Xiang Zhong can be obtained by liquid separation, recycling design：
In above-mentioned II preparation method of ligand, the molar ratio 1 of ligand A and trimethyl aluminium：1~1.3, preferably 1：1~1.05.
In above-mentioned II preparation method of ligand, the organic solvent is dry hexane, toluene and one kind in hexamethylene or
Two kinds, preferably dry hexane or toluene.
In above-mentioned II preparation method of ligand, consumption of organic solvent is reaction raw materials（Ligand A and trimethyl aluminium）The 5 of gross mass
~40 times.
It in above-mentioned II preparation method of ligand, reacts and is carried out under gas shield, the gas is inert gas or nitrogen.
In above-mentioned II preparation method of ligand, reaction nature rises to 30~110 again after being raised to room temperatureoC is reacted, such as
30oC、40oC、50oC、60oC、70oC、80oC、90oC、100oC、110oC is preferably raised to 40~60oC is reacted.30~
110oC（It is preferred that 40~60oC）The time reacted is 1~12 hour, preferably 3~6 hours.
In above-mentioned II preparation method of ligand, after reaction, water is added in into reaction solution, liquid separation is stood after being sufficiently mixed.
The dosage of water is the mole of 3 times or so of ligand A.After standing liquid separation, gained organic phase is spin-dried for solvent, remaining crude product first
One or both of alcohol, ethyl alcohol are recrystallized, you can obtain II ligand of formula, II product.
Formula A and the ligand of formula II can react to form aluminium with trimethyl aluminium with N, N, O, O quad-tree index
Complex, gained aluminum complex structural formula is as shown in following formula I, and in formula I, R is the alkane or halogen of hydrogen, C1-C4, and the halogen is
Fluorine, chlorine, bromine or iodine.R is preferably tertiary butyl or bromine.
Aluminum complex shown in the above-mentioned formula I of the present invention, can be prepared as the ligand II shown in formula II with trimethyl aluminium,
It can also be generated during synthetic ligands II, be reacted and be made with trimethyl aluminium with ligand A, specific preparation method includes
Following steps：Ligand A or ligand II are added in organic solvent, -10~0 oTrimethyl aluminium is added under C, makes reaction after adding
Temperature is warmed to room temperature naturally, and temperature then is risen to 30~110oC is reacted, and vacuum drains solvent, washing, mistake after reaction
Filter, obtains the aluminum complex described in formula I.
In above-mentioned aluminum complex preparation method, the molar ratio 1 of ligand A or ligand II and trimethyl aluminium：1~1.3, preferably 1：
1~1.05.
In above-mentioned aluminum complex preparation method, the organic solvent is one kind in dry hexane, toluene and hexamethylene
Or two kinds, preferably hexane or toluene.Consumption of organic solvent is reaction raw materials（Ligand A or ligand II and trimethyl aluminium）Gross mass
5~40 times.
In above-mentioned aluminum complex preparation method, reaction nature rises to 30~110 again after being raised to room temperatureoC is reacted, example
Such as 30oC、40oC、50oC、60oC、70oC、80oC、90oC、100oC、110oC is preferably raised to 40~60oC is reacted.30~
110oC（It is preferred that 40~60oC）The time reacted is 1~12 hour, preferably 3~6 hours.
It in above-mentioned aluminum complex preparation method, reacts and is carried out under gas shield, the gas is inert gas or nitrogen.
After reaction solution is spin-dried for solvent, residue is washed with n-hexane, is then dried, you can obtains the aluminum complex described in formula I.
Aluminum complex shown in the above-mentioned formula I of the present invention can be urged with being used as the catalyst of cyclic lactone ring-opening polymerization
The ring-opening polymerisation of a variety of cyclic lactones such as outside the pale of civilization meso-lactide, Study of Meso-Lactide, levorotatory lactide, caprolactone, glycolide.It should
During catalyst cyclic lactone ring-opening polymerization, with catalytic activity is high, stereoselectivity is good, reaction rate is fast, molecular weight
The advantages that controllability is high particularly can obtain the high isotactic poly of fusing point third when being catalyzed rac-lactide polymerization and hand over
Ester, shows higher stereoselectivity, and stereoselectivity reaches as high asP m = 0.83.In catalysis lactide, caprolactone and second
During lactide, obtained polymer is the polymer of benzyloxy sealing end.Therefore, the ligand of the aldehyde radical of the invention containing bigcatkin willow is as cyclic lactone
The application of the ligand of the catalyst of ring-opening polymerization is also within the scope of the present invention.
When using the aluminum complex described in formula I as catalyst, cyclic lactone ring-opening polymerization specifically includes following steps：It will
Aluminum complex, organic solvent, alcohol co-catalyst and cyclic lactone mixing described in formula I, carry out under anhydrous and oxygen-free and gas shield
Ring-opening polymerization is handled reactant after reaction, obtains polylactone.
In above-mentioned ring-opening polymerization, organic solvent used in reaction is toluene or tetrahydrofuran, preferably toluene.Used in reaction
Alcohol co-catalyst is benzylalcohol.
In above-mentioned ring-opening polymerization, the molar ratio of cyclic lactone and catalyst is 50~1500：1, such as 50:1、100：1、
150:1、200:1、300:1、400:1、500:1、600：1、800:1、1000:1、1200:1、1500：1.Alcohol co-catalyst is with urging
The molar ratio of agent is 1~3：1.
In above-mentioned ring-opening polymerization, polymeric reaction temperature be 20~110 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60
℃、70℃、80℃、90℃、100℃、110℃.With the raising of polymeric reaction temperature, the stereoselectivity of catalyst has reduction
Trend, catalytic activity has raised trend, when reaction temperature is at 80 DEG C, stood when being catalyzed to rac-lactide
Body is selectively reachableP m =0.64, when reaction temperature is at 20 DEG C, stereoselectivity when being catalyzed to rac-lactide
It is reachableP m= 0.83。
In above-mentioned ring-opening polymerization, polymerization reaction time be 1-1440 minutes, such as 1 minute, 10 minutes, 30 minutes,
40 minutes, 60 minutes, 120 minutes, 240 minutes, 600 minutes, 900 minutes, 1200 minutes, 1440 minutes etc..
Cold methanol purifying polylactone is added in above-mentioned ring-opening polymerization, after reaction, obtains polylactone after purification.
The present invention provides the ligand of two kinds of aldehyde radicals containing bigcatkin willow, which can be with N, N, O, O quad-tree index, energy and trimethyl
Aluminium is complexed to form complex.Ligand structure of the present invention is special, and preparation method is simple, and the aluminum complex of formation can be used as cyclic lactone
The catalyst of ring-opening polymerization, the catalyst activity is high, and stereoselectivity is high, and reaction rate quickly, grasp by polymerisation
Make simply, and can controllably obtain the product of different molecular weight, selectivity is wide, there are good market prospects.
Specific embodiment
It is further illustrated the present invention below by specific embodiment, but the present invention is not limited thereto, specific protection domain is shown in
Claim.
In following embodiments, the stereoselectivity of isotaxy polylactide is carried out using nuclear magnetic resonance same core decoupling hydrogen spectrum
Test.
Prepare the ethylenediamine (a) of unilateral protection
0.50 g p-methyl benzenesulfonic acid is dissolved into dimethylbenzene, is first slowly added into the ethylenediamine of p-methyl benzenesulfonic acid equimolar amounts, then
The phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, heating reflux reaction 8h are added in, reaction is cooled to room temperature after terminating will
Solid filters, and washing is dried to obtain solid.Solid is dissolved into dichloromethane, the full of excessive sodium bicarbonate is slowly added dropwise
And aqueous solution, room temperature reaction, after reaction liquid separation are dried with anhydrous magnesium sulfate, are spin-dried for solvent, obtain unilateral phthalic acid
0.48 g of ethylenediamine of acid anhydride protection, yield 87.3%.Reaction equation is as follows：
Prepare the ligand of the aldehyde radical containing bigcatkin willow（A）
The ligand of the aldehyde radical containing bigcatkin willow is to be obtained by the ethylenediamine of unilateral protection and salicylide or derivatives thereof by condensation reaction,
It illustrates below to synthesizing different ligand A.
Embodiment 1
Synthesized ligand structure formula such as above formula（A）, wherein R is hydrogen, and reaction process is：By the ethylenediamine of unilateral protection（a）0.20
The salicylide of g and equimolar amounts add in 10 mL methanol in, heating reflux reaction 12 hours, reaction terminate after cold filtration simultaneously
It is washed, filtered with cold methanol, collected and drying is weighed, obtain 0.27 g solids, yield 87.1%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.85 (s, 1H, OH), 8.26 (s, 1H, ArHC=N), 7.80
(d, J = 5.4 Hz, 2H, Ar–H), 7.68 (d, J = 5.4Hz, 2H, Ar–H), 7.24–7.16 (m, 1H,
Ar–H), 7.11 (m, 1H, Ar–H), 6.97 (d, J = 8.3 Hz, 1H, Ar–H), 6.75 (td, J = 7.5,
1.0 Hz, 1H, Ar–H), 4.20 (m, 2H, NCH 2), 4.10 (m, 2H, NCH 2). HRESI-MS: m/z
cacld. C17H14N2O3 [M-H]-; 293.0927, found: 293.0931.
Can be seen that products obtained therefrom from more than characterization result is above formula（A）Middle R is the ligand of hydrogen.
Embodiment 2
Synthesized ligand structure formula such as above formula（A）, wherein R is methyl, and reaction process is：By the ethylenediamine of unilateral protection（a）
3, the 5- dimethyl salicylide of 0.25 g and equimolar amounts is added in 20 mL methanol, and heating reflux reaction 12 hours, reaction terminates
Later cold filtration is simultaneously washed with cold methanol, is filtered, and collects and drying is weighed, obtain 0.38 g solids, yield 90.5%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ 12.61 (s, 1H, OH), 8.20 (s, 1H, ArHC=N), 7.73
(d, J = 5.5 Hz, 2H, Ar–H), 7.66 (d, J = 5.4 Hz, 2H, Ar–H), 6.96 (s, 1H, Ar–H), 6.75 (s, 1H, Ar–H), 4.31– 4.28(m, 2H, NCH 2), 4.20–4.15 (m, 2H, NCH 2), 2.17
(s, 3H, CH 3), 2.15 (s, 3H, CH 3)。HRESI-MS: m/z cacld. C19H18N2O3 [M-H]-;
321.1238, found: 321.1236.
Can be seen that products obtained therefrom from more than characterization result is above formula（A）Middle R is the ligand of methyl.
Embodiment 3
Synthesized ligand structure formula such as above formula（A）, wherein R is bromine, and reaction process is：By the ethylenediamine of unilateral protection（a）0.22
3, the 5- Dibromosalicylaldehydes of g and equimolar amounts are added in 15 mL methanol, heating reflux reaction 12 hours, and reaction is cold after terminating
But it filters and is washed with cold methanol, filtered, collect and drying is weighed, obtain 0.46 g solids, yield 88.5%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ 13.90 (s, 1H, OH), 8.19 (s, 1H, ArHC=N), 7.82–
7.74(m, 2H, Ar–H), 7.67–7.60 (m, 2H, Ar–H), 7.54 (s, 1H, Ar–H), 7.15 (s, 1H,
Ar–H), 4.30–4.27 (m, 2H, NCH 2), 4.25–4.20 (m, 2H, NCH 2)。HRESI-MS: m/z cacld.
C17H12Br2N2O3 [M-H]-; 448.9136, found: 448.9138.
Can be seen that products obtained therefrom from more than characterization result is above formula（A）Middle R is the ligand of bromine.
Embodiment 4
Synthesized ligand structure formula such as above formula（A）, wherein R is tertiary butyl, and reaction process is：By the ethylenediamine of unilateral protection（a）
3, the 5- di-tert-butyl salicylaldehydes of 0.30 g and equimolar amounts are added in 20 mL methanol, heating reflux reaction 12 hours, reaction knot
Shu Yihou cold filtrations are simultaneously washed with cold methanol, filtering, collect and drying is weighed, obtain 0.53 g solids, yield 82.8%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ13.27 (s, 1H, OH), 8.23 (s, 1H, ArHC=N), 7.70–
7.68 (m, 2H, Ar–H) ), 7.64–7.59 (m, 2H, Ar–H), 7.30 (s, 1H, Ar–H)), 6.95 (s,
2H, Ar–H)), 4.34–4.29 (m, 2H, NCH 2), 4.13–4.10 (m, 2H, NCH 2), 1.37 (s, 9H,
CH3), 1.26(s, 9H, CH3)。HRESI-MS: m/z cacld. C25H30N2O3 [M-H]-; 405.2175, found:
405.2173.
Can be seen that products obtained therefrom from more than characterization result is above formula（A）Middle R is the ligand of tertiary butyl.
Prepare the ligand of the aldehyde radical containing bigcatkin willow（Ⅱ）
The ligand of the aldehyde radical containing bigcatkin willow（Ⅱ）It is synthesized according to following routes, R is the alkane or halogen of hydrogen, C1-C4, is simply enumerated below
The preparation process of several ligands II.
Embodiment 5
R is that the ligand II of hydrogen synthesizes：In a nitrogen atmosphere, by ligand A（R is hydrogen）0.30 g is dissolved in 10 mL dry toluenes,
The trimethyl aluminium of ligand 1.0 times of moles of A is added at -10 DEG C, after reaction temperature is raised to room temperature naturally, is heated to 60 DEG C
Reaction 4 hours after reaction terminates, adds in 55 microlitres of water and stops reaction, organic phase, anhydrous sodium sulfate drying, rotation are collected in liquid separation
Dry solvent, obtains crude product, by crude product through recrystallizing methanol, obtains 0.27 g of net product, 84.4 % of yield.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.85 (s, 1H, OH), 8.31 (s, 1H, CH=N), 7.61 (d,
J = 7.5 Hz, 1H, Ar–H), 7.55–7.47 (m, 4H, Ar–H), 7.15 (d, J = 7.4 Hz, 1H, Ar–H), 6.88 (d, J = 8.2 Hz, 1H, Ar–H), 6.65 (t, J = 7.4 Hz, 1H, Ar–H), 4.41–4.32
(m, 2H, NCH 2), 4.16–4.10 (m, 2H, NCH), 1.61 (s, 3H, CH3).
HRESI-MS: m/z cacld. C18H18N2O3 [M-H]-; 309.1238, found: 309.1236.
Can be seen that products obtained therefrom from more than characterization result is above formula（Ⅱ）Middle R is the ligand of hydrogen.
Embodiment 6
R is that the ligand II of methyl synthesizes：Under nitrogen atmosphere, by ligand A（R is methyl）0.40 g is dissolved in 10 mL drying hexamethylenes
In, the trimethyl aluminium of ligand 1.05 times of moles of A is added at 0 DEG C, after reaction temperature is raised to room temperature naturally, heating is reacted
Temperature is reacted 6 hours to 40 DEG C, and 67 microlitres of water are added in after reaction and stop reacting, liquid separation collection organic phase, anhydrous sodium sulfate drying,
Solvent is spin-dried for, obtains crude product, by crude product through recrystallizing methanol, obtains 0.36 g of net product, yield 85.7%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ13.01 (s, 1H, OH), 8.27 (s, 1H, CH=N), 7.64 (d, J
= 7.4 Hz, 1H, Ar–H), 7.55–7.44 (m, 3H, Ar–H), 6.98–6.88 (m, 1H, Ar–H), 6.81–
6.72 (m, 1H, Ar–H), 4.38–4.31 (m, 2H, NCH2), 4.18–4.09 (m, 2H, NCH2), 2.21
(s, 6H, ArCH3), 1.61 (s, 3H, CH3). HRESI-MS: m/z cacld. C20H22N2O3 [M-H]-;
337.1553, found: 337.1556.
Can be seen that products obtained therefrom from more than characterization result is above formula（Ⅱ）Middle R is the ligand of methyl.
Embodiment 7
R is that the ligand II of bromine synthesizes：Under nitrogen atmosphere, by ligand A（R is bromine）0.30 g is dissolved in 10 mL dry toluenes ,-
The trimethyl aluminium of ligand 1.1 times of moles of A is added at 5 DEG C, after reaction temperature is raised to room temperature naturally, is heated to 110 DEG C of reactions
1 hour, reaction added in 36 microlitres of water and stops reaction after terminating, organic phase is collected in liquid separation, and anhydrous sodium sulfate drying is spin-dried for molten
Agent obtains crude product, by crude product through ethyl alcohol recrystallization, obtains 0.26 g of net product, yield 83.9%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.56 (s, 1H, OH), 8.27 (s, 1H, CH=N), 7.63–7.58
(m, 2H, Ar–H), 7.41–7.30 (m, 2H, Ar–H), 7.16 (d, J = 7.2 Hz, 1H, Ar–H), 7.12
(d, J = 7.2 Hz, 1H, Ar–H), 4.45–4.32 (m, 2H, NCH 2), 4.23–4.14 (m, 2H, NCH 2),
1.60 (s, 3H, CH3).
HRESI-MS: m/z cacld. C18H16Br2N2O3 [M-H]-; 464.9448, found: 464.9452.
Can be seen that products obtained therefrom from more than characterization result is above formula（Ⅱ）Middle R is the ligand of bromine.
Embodiment 8
R is that the ligand II of tertiary butyl synthesizes：Under nitrogen atmosphere, by ligand A（R is tertiary butyl）0.20 g is being dissolved in 8 mL dryings just
In hexane, the trimethyl aluminium of ligand 1.3 times of moles of A is added at -5 DEG C, after reaction temperature is raised to room temperature naturally, heating
It is reacted 8 hours to 30 DEG C, 27 microlitres of water is added in after reaction and stop reaction, organic phase is collected in liquid separation, and anhydrous sodium sulfate drying is spin-dried for
Solvent obtains crude product, by crude product through recrystallizing methanol, obtains 0.17 g of net product, yield 81.0%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (300 MHz, CDCl3) δ13.02 (s, 1H, OH), 8.24 (s, 1H, CH=N), 7.76–7.65
(m, 1H, Ar–H), 7.63–7.52 (m, 3H, Ar–H), 7.50–7.42(m, 1H, Ar–H), 7.40 (d, J =
7.2 Hz, 1H, Ar–H), 7.18 (d, J = 7.0 Hz, 1H, Ar–H), 7.08–7.00 (m, 1H, Ar–H),
4.35–4.21 (m, 2H, NCH 2), 4.14–4.06 (m, 2H, NCH 2), 1.62(s, 3H, CH3), 1.38 (s,
9H, CH3), 1.24 (s, 9H, CH3).
HRESI-MS: m/z cacld. C26H34N2O3 [M-H]-; 421.2492, found: 421.2487.
Can be seen that products obtained therefrom from more than characterization result is above formula（Ⅱ）Middle R is the ligand of tertiary butyl.
Aluminum complex is prepared using ligand A as raw material（I）
Formula（I）Shown aluminum complex is eliminated by ligand A and trimethyl aluminium by alkyl and alkyl addition reaction generates, and reaction equation is such as
Under.
Embodiment 9
Ligand structure formula such as above formula used（A）, wherein R is hydrogen, and reaction process is：In a nitrogen atmosphere, by 0.21 g of ligand A
It is dissolved in 8 mL dry toluenes, the trimethyl aluminium of ligand 1.0 times of moles of A is added at -10 DEG C, treats that reaction temperature rises naturally
It to after room temperature, is heated to 100 DEG C and reacts 1 hour, vacuum drains solvent after reaction terminates, and adds in dry n-hexane filtering simultaneously
It is washed, filtered with dry n-hexane, collected and drying is weighed, obtain 0.22 g solids, yield 88.0%.
Products therefrom nuclear-magnetism information is as follows, and the compound that R is hydrogen is can be seen that from nuclear-magnetism information（I）It synthesizes successfully.
1H NMR (400 MHz, CDCl3) δ 8.22 (s, 1H, ArHC=N), 7.61 (d, J = 6.7 Hz,
1H, Ar–H), 7.53 (d, J = 6.7 Hz, 1H, Ar–H), 7.41 (t, J = 7.1 Hz, 1H, Ar–H),
7.33 (d, J = 6.3 Hz, 1H, Ar–H), 7.08 (d, J = 7.1 Hz, 1H, Ar–H), 6.76–6.62 (m,
3H, Ar–H), 4.25–4.20 (m, 2H, NCH 2), 4.13–4.08 (m, 2H, NCH 2), 1.65 (s, 3H,
CH 3),–0.50(s, 3H, AlCH3). Anal. Calcd for C19H19AlN2O3: C 65.14, H 5.47, N 8.00.
Found: C 65.16, H 5.49, N 8.05.
Embodiment 10
Ligand structure formula such as above formula used（A）, wherein R is methyl, and reaction process is：Under nitrogen atmosphere, by 0.41 g of ligand A
It is dissolved in 12 mL drying hexamethylenes, the trimethyl aluminium of ligand 1.05 times of moles of A is added at 0 DEG C, treats reaction temperature nature
After being raised to room temperature, heating reaction temperature to 60 DEG C react 4 hours, reaction terminate after vacuum drain solvent, add in it is dry just
Hexane is filtered and is washed with dry n-hexane, is filtered, and collects and drying is weighed, obtain 0.39 g solids, yield 81.2%.
Products therefrom nuclear-magnetism information is as follows, and the compound that R is methyl is can be seen that from nuclear-magnetism information（I）It synthesizes successfully.
1H NMR (400 MHz, CDCl3) δ8.17 (s, 1H, ArHC=N), 7.68 (s, 1H, Ar–H),
7.61–7.57 (m, 2H, Ar–H), 7.13 (s, 1H, Ar–H), 6.30 (s, 1H, Ar–H), 4.32 (m, 2H,
NCH2), 4.13 (m, 2H, NCH2), 2.14–2.10 (m, 2H, CH2CH 2), 2.10 (s, 3H, ArCH 3),
2.08 (s, 3H, ArCH 3), 1.67 (s, 3H, CCH 3), –0.50 (s, 3H, AlCH 3). Anal. Calcd for
C21H23AlN2O3: C 66.66, H 6.13, N 7.40. Found: C 66.61, H 6.18, N 7.45.
Embodiment 11
Ligand structure formula such as above formula used（A）, wherein R is bromine, and reaction process is：Under nitrogen atmosphere, it is 0.24 g of ligand A is molten
In 10 mL dry toluenes, the trimethyl aluminium of ligand 1.1 times of moles of A is added at -5 DEG C, treats that reaction temperature is raised to naturally
It after room temperature, is heated to 50 DEG C and reacts 5 hours, vacuum drains solvent after reaction terminates, and adds in dry n-hexane and filters and is used in combination
Dry n-hexane washing, filtering, is collected and drying is weighed, and obtains 0.24 g solids, yield 88.9%.
The nuclear-magnetism information of products obtained therefrom is as follows, it can be seen that R is the compound of bromine（I）It synthesizes successfully.
1H NMR (400 MHz, CDCl3) δ 8.21 (s, 1H, ArHC=N), 7.84 (d, J = 6.7 Hz,
1H, Ar–H), 7.66 (s, 2H, Ar–H), 7.64–7.55 (m, 2H, Ar–H), 7.40–7.33 (m, 1H, Ar–H), 4.27 (m, 2H, NCH 2), 4.10–4.06 (m, 2H, NCH 2), 1.67 (s, 1H, CCH 3), –0.50 (s,
3H, AlCH 3). Anal. Calcd for C19H17AlBr2N2O3: C 44.91, H 3.37, N 5.51. Found: C
44.93, H 3.41, N 5.55.
Embodiment 12
Ligand structure formula such as above formula used（A）, wherein R is tertiary butyl, and reaction process is：Under nitrogen atmosphere, by ligand A 0.23
G is dissolved in 10 mL drying n-hexanes, and the trimethyl aluminium of ligand 1.0 times of moles of A is added at -10 DEG C, treats reaction temperature certainly
It after being so raised to room temperature, is heated to 40 DEG C and reacts 12 hours, filter and weighed with dry n-hexane filter wash cake, collection and drying,
Obtain 0.24 g solids, yield 92.3%.
The nuclear-magnetism information of products therefrom is as follows, it can be seen that R is the compound of tertiary butyl（I）It synthesizes successfully.
1H NMR (400 MHz, CDCl3) δ 8.17 (s, 1H, ArHC=N), 7.80 (d, J = 6.7 Hz,
1H, Ar–H), 7.67 (s, 2H, Ar–H), 7.60–7.53 (m, 2H, Ar–H), 7.41–7.32 (m, 1H, Ar–H), 4.33–4.29 (m, 2H, NCH 2), 3.93–3.86 (m, 2H, NCH 2), 1.66 (s, 3H, CCH 3), 1.31
(s, 9H, CH3), 1.24(s, 9H, CH3), –0.52 (s, 3H, AlCH 3). Anal. Calcd for
C27H35AlN2O3: C 70.11, H 7.63, N 6.06. Found: C 70.12, H 7.65, N 6.12.
Aluminum complex is prepared for raw material with ligand II（I）
Embodiment 13
Ligand structure formula such as above formula used（II）, wherein R is hydrogen, and reaction process is：In a nitrogen atmosphere, by ligand i I 0.30
G is dissolved in 10 mL drying hexamethylenes, and the trimethyl aluminium of ligand i 1.2 times of moles of I is added at -10 DEG C, treats reaction temperature certainly
It after being so raised to room temperature, is heated to 40 DEG C and reacts 6 hours, reaction is filtered after terminating and washed with dry n-hexane, is filtered, and is received
Collect and dry and weigh, obtain 0.29 g solids, yield 85.3%.For product structure formula as shown in formula I, R is hydrogen.
Embodiment 14
Ligand structure formula such as above formula used（II）, wherein R is methyl, and reaction process is：Under nitrogen atmosphere, by ligand i I 0.25
G is dissolved in 10 mL dry toluenes, and the trimethyl aluminium of ligand i 1.1 times of moles of I is added at 0 DEG C, treats that reaction temperature rises naturally
To after room temperature, heating reaction temperature to 110 DEG C react 1 hour, reaction terminate after vacuum drain solvent, add in it is dry just
Hexane is filtered and is washed with dry n-hexane, is filtered, and collects and drying is weighed, obtain 0.20 g solids, yield 71.4%.Production
For object structural formula as shown in formula I, R is methyl.
Embodiment 15
Ligand structure formula such as above formula used（II）, wherein R is bromine, and reaction process is：Under nitrogen atmosphere, by 0.45 g of ligand i I
It is dissolved in 15 mL drying hexanes, the trimethyl aluminium of ligand i 1.0 times of moles of I is added at -5 DEG C, treats that reaction temperature rises naturally
It to after room temperature, is heated to 60 DEG C and reacts 3 hours, reaction is filtered after terminating and washed with dry n-hexane, is filtered, and is collected
And drying is weighed, and obtains 0.41 g solids, yield 83.7%.For product structure formula as shown in formula I, R is bromine.
Embodiment 16
Ligand structure formula such as above formula used（II）, wherein R is tertiary butyl, and reaction process is：Under nitrogen atmosphere, by ligand i I
0.40 g is dissolved in 12 mL dry toluenes, and the trimethyl aluminium of ligand i 1.1 times of moles of I is added at 0 DEG C, treats reaction temperature
Naturally after being raised to room temperature, 60 DEG C is heated to and is reacted 2 hours, reaction is filtered and washed with dry n-hexane, mistake after terminating
Filter, is collected and drying is weighed, and obtains 0.40 g solids, yield 90.9%.For product structure formula as shown in formula I, R is tertiary butyl.
Prepare polyglycolide
Embodiment 17
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 100 μm of ol catalyst（Aluminum complex shown in formula I, R are hydrogen）, 100 μm of ol benzylalcohols, 20 mL toluene and 10 mmol
Glycolide, be subsequently placed in 110oIn the oil bath of C, reaction adds in a small amount of water and terminates reaction after 12 minutes, with ethanol precipitation, washing
For several times, it is dried in vacuo at room temperature, obtains 1.09 g products, yield 94.0%, molecular weight 2.2 ten thousand.
Embodiment 18
Polyglycolide is prepared according to the method for embodiment 17, unlike：Catalyst used is aluminum complex, R shown in formula I
For methyl.The quality of products obtained therefrom is 1.10 g after reaction 14 minutes, and yield 94.8%, molecular weight is 2.3 ten thousand.
Embodiment 19
Polyglycolide is prepared according to the method for embodiment 17, unlike：Catalyst used is aluminum complex, R shown in formula I
For bromine.The quality of products obtained therefrom is 1.12 g after reaction 7 minutes, and yield 96.6%, molecular weight is 2.1 ten thousand.
Embodiment 20
Polyglycolide is prepared according to the method for embodiment 17, unlike：Catalyst used is aluminum complex, R shown in formula I
For tertiary butyl.The quality of products obtained therefrom is 1.10 g after reaction 15 minutes, and yield 94.8%, molecular weight is 2.0 ten thousand.
Embodiment 21
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 100 μm of ol catalyst（Aluminum complex shown in formula I, R are bromine）, 100 μm of ol benzylalcohols, 20 mL toluene and 10 mmol
Glycolide, then respectively 20oC、40oC、60oC、80oC and 100oIt is reacted under C, adds in a small amount of water after reaction and terminate instead
Should, with methanol extraction, washing for several times, it is dried in vacuo at room temperature.
Wherein, it is reacted 18 hours at 20 DEG C, obtains 1.10 g products, yield 94.8%, molecular weight 2.1 ten thousand.
It is reacted 9 hours at 40 DEG C, obtains 1.11 g products, yield 95.7%, molecular weight 2.3 ten thousand.
It is reacted 5 hours at 60 DEG C, obtains 1.09 g products, yield 94.0%, molecular weight 2.0 ten thousand.
It is reacted 40 minutes at 80 DEG C, obtains 1.10 g products, yield 94.8%, molecular weight 2.2 ten thousand.
It is reacted 15 minutes at 100 DEG C, obtains 1.11 g products, yield 95.7%, molecular weight 2.1 ten thousand.
Embodiment 22
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 10 μm of ol catalyst（Aluminum complex shown in formula I, R are hydrogen）, 30 μm of ol benzylalcohols, 10 mL tetrahydrofurans and 15
The glycolide of mmol, then 30oC adds in a small amount of water and terminates reaction after reacting 16 hours, with methanol extraction, washing for several times, room temperature
Lower vacuum drying obtains 1.68 g products, yield 96.6%, molecular weight 13.3 ten thousand.
Embodiment 23
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 10 μm of ol catalyst（Aluminum complex shown in formula I, R methyl）, 20 μm of ol benzylalcohols, 20 mL tetrahydrofurans and 10
The glycolide of mmol, is subsequently placed in 50oIn the oil bath of C, reaction adds in a small amount of water and terminates reaction after 8 hours, with ethanol precipitation, wash
It washs for several times, is dried in vacuo at room temperature, obtain 1.10 g products, yield 94.8%, molecular weight 14.0 ten thousand.
Embodiment 24
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 200 μm of ol catalyst（Aluminum complex shown in formula I, R are tertiary butyl）, 200 μm of ol benzylalcohols, 10 mL toluene and 10
The glycolide of mmol, is subsequently placed in 70oIn the oil bath of C, reaction adds in a small amount of water and terminates reaction after 4 hours, with methanol extraction, wash
It washs for several times, is dried in vacuo at room temperature, obtain 1.10 g products, yield 94.8%, molecular weight 1.1 ten thousand.
Embodiment 25
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 10 μm of ol catalyst（Aluminum complex shown in formula I, R are hydrogen）, 20 μm of ol benzylalcohols, 15 mL toluene and 5 mmol second
Lactide, then 90oC adds in a small amount of water and terminates reaction after reacting 5 hours, with methanol extraction, washing for several times, vacuum is done at room temperature
It is dry, obtain 0.54 g products, yield 93.1%, molecular weight 6.7 ten thousand.
Prepare poly-epsilon-caprolactone
Embodiment 26
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 100 μm of ol catalyst（Aluminum complex shown in formula I, R are hydrogen）, 100 μm of ol benzylalcohols, 10 mL toluene and 10 mmol
Caprolactone, be subsequently placed in 110oIn the oil bath of C, reaction adds in a small amount of water and terminates reaction after five minutes, with ethanol precipitation, washing
For several times, it is dried in vacuo at room temperature, obtains 1.11 g products, yield 97.4%, molecular weight 2.4 ten thousand.
Embodiment 27
Method according to embodiment 26 prepares polycaprolactone, unlike：Catalyst used is aluminum complex, R shown in formula I
For methyl.The quality of products obtained therefrom is 1.10 g after reaction 6 minutes, and yield 96.5%, molecular weight is 2.0 ten thousand.
Embodiment 28
Method according to embodiment 26 prepares polycaprolactone, unlike：Catalyst used is aluminum complex, R shown in formula I
For bromine.The quality of products obtained therefrom is 1.12 g after reaction 1.5 minutes, and yield 98.2%, molecular weight is 2.2 ten thousand.
Embodiment 29
Method according to embodiment 26 prepares polycaprolactone, unlike：Catalyst used is aluminum complex, R shown in formula I
For tertiary butyl.The quality of products obtained therefrom is 1.10 g after reaction 7 minutes, and yield 96.5%, molecular weight is 2.3 ten thousand.
Embodiment 30
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 100 μm of ol catalyst（Aluminum complex shown in formula I, R are bromine）, 100 μm of ol benzylalcohols, 10 mL toluene and 10 mmol
Caprolactone, then respectively 20oC、40oC、60oC、80oC and 100oIt is reacted under C, adds in a small amount of water after reaction and terminate instead
Should, with methanol extraction, washing for several times, it is dried in vacuo at room temperature.
Wherein, it is reacted 35 minutes at 20 DEG C, obtains 1.10 g products, yield 96.5%, molecular weight 2.0 ten thousand.
It is reacted 18 minutes at 40 DEG C, obtains 1.10 g products, yield 96.5%, molecular weight 2.3 ten thousand.
It is reacted 12 minutes at 60 DEG C, obtains 1.11 g products, yield 97.4%, molecular weight 2.1 ten thousand.
It is reacted 9 minutes at 80 DEG C, obtains 1.11 g products, yield 97.4%, molecular weight 2.2 ten thousand.
It is reacted 3 minutes at 100 DEG C, obtains 1.12 g products, yield 98.2%, molecular weight 2.4 ten thousand.
Embodiment 31
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 10 μm of ol catalyst（Aluminum complex shown in formula I, R are hydrogen）, 30 μm of ol benzylalcohols, 10 mL tetrahydrofurans and 5 mmol
6-caprolactone, then 30oC adds in a small amount of water and terminates reaction after reacting 50 minutes, with ethanol precipitation, washing for several times, at room temperature
Vacuum drying, obtains 0.54 g products, yield 94.7%, molecular weight 5.8 ten thousand.
Embodiment 32
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 10 μm of ol catalyst（Aluminum complex shown in formula I, R are methyl）, 30 μm of ol benzylalcohols, 10 mL toluene and 10 mmol
6-caprolactone, then 50oC reactions add in a small amount of water and terminate reaction after twenty minutes, with ethanol precipitation, washing for several times, at room temperature
Vacuum drying, obtains 1.12 g products, yield 98.2%, molecular weight 7.4 ten thousand.
Embodiment 33
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 10 μm of ol catalyst（Aluminum complex shown in formula I, R are tertiary butyl）, 20 μm of ol benzylalcohols, 15 mL toluene and 15
The 6-caprolactone of mmol, is subsequently placed in 90oIn the oil bath of C, reaction adds in a small amount of water and terminates reaction after 9 minutes, with ethanol precipitation,
Washing for several times, is dried in vacuo, obtains 1.63 g products, yield 95.3%, molecular weight 15.8 ten thousand at room temperature.
Embodiment 34
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 100 μm of ol catalyst（Aluminum complex shown in formula I, R are hydrogen）, 100 μm of ol benzylalcohols, 10 mL toluene and 5 mmol
6-caprolactone, be subsequently placed in 70oIn the oil bath of C, reaction adds in a small amount of water and terminates reaction after 11 minutes, with ethanol precipitation, wash
It washs for several times, is dried in vacuo at room temperature, obtain 0.55 g products, yield 96.5%, molecular weight 1.0 ten thousand.
Prepare polylactide
Embodiment 35
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 100 μm of ol catalyst（Aluminum complex shown in formula I, R are hydrogen）, 100 μm of ol benzylalcohols, 20 mL toluene and 10 mmol
Rac-lactide, then 20oC adds in a small amount of water and terminates reaction after reacting 21 hours, with ethanol precipitation, washing for several times, room
Temperature is lower to be dried in vacuo, and obtains 1.34 g products, yield 93.1%.Products therefrom be isotaxy polylactide, molecular weight 2.8 ten thousand,
Isotaxy stereoselectivityP m= 0.77。
Embodiment 36
Method according to embodiment 35 prepares polylactide, unlike：Catalyst used is aluminum complex, R shown in formula I
For methyl.Reaction adds in a small amount of water and terminates reaction after 22 hours, with ethanol precipitation, washing for several times, be dried in vacuo at room temperature.Institute
The quality for obtaining product is 1.36 g, and yield 94.4%, molecular weight is 2.9 ten thousand, isotaxy stereoselectivityP m= 0.81。
Embodiment 37
Method according to embodiment 35 prepares polylactide, unlike：Catalyst used is aluminum complex, R shown in formula I
For bromine.Reaction adds in a small amount of water and terminates reaction after 20 hours, with ethanol precipitation, washing for several times, be dried in vacuo at room temperature.Gained
The quality of product is 1.42 g, and yield 98.6%, molecular weight is 2.6 ten thousand, isotaxy stereoselectivityP m= 0.80。
Embodiment 38
Method according to embodiment 35 prepares polylactide, unlike：Catalyst used is aluminum complex, R shown in formula I
For tertiary butyl.Reaction adds in a small amount of water and terminates reaction after 24 hours, with ethanol precipitation, washing for several times, be dried in vacuo at room temperature.
The quality of products obtained therefrom is 1.40 g, and yield 97.2%, molecular weight is 2.7 ten thousand, isotaxy stereoselectivityP m= 0.83。
Embodiment 39
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 100 μm of ol catalyst（Aluminum complex shown in formula I, R are tertiary butyl）, 100 μm of ol benzylalcohols, 10 mL toluene and 10
The rac-lactide of mmol, then respectively 40oC、60oC and 80oIt is reacted under C, adds in a small amount of water after reaction and terminate instead
Should, with methanol extraction, washing for several times, it is dried in vacuo at room temperature.
Wherein, it is reacted 21 hours at 40 DEG C, obtains 1.40 g products, yield 97.2%, molecular weight 2.8 ten thousand,P m = 0.78。
It is reacted 17 hours at 60 DEG C, obtains 1.41 g products, yield 97.9%, molecular weight 2.6 ten thousand,P m = 0.71。
It is reacted 14 hours at 80 DEG C, obtains 1.41 g products, yield 97.9%, molecular weight 2.7 ten thousand,P m = 0.64。
Embodiment 40
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 200 μm of ol catalyst（Aluminum complex shown in formula I, R are hydrogen）, 200 μm of ol benzylalcohols, 20 mL tetrahydrofurans and 10
The levorotatory lactide of mmol, then 30oC adds in a small amount of water and terminates reaction after reacting 20 hours, with ethanol precipitation, washing for several times,
It is dried in vacuo at room temperature, obtains 1.40 g products, yield 97.2%, molecular weight 1.1 ten thousand.
Embodiment 41
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 10 μm of ol catalyst（Aluminum complex shown in formula I, R are methyl）, 10 μm of ol benzylalcohols, 10 mL tetrahydrofurans and 5
The Study of Meso-Lactide of mmol, is subsequently placed in 50oIn the oil bath of C, reaction adds in a small amount of water and terminates reaction after 17 hours, use ethyl alcohol
Precipitation, washing for several times, are dried in vacuo, obtain 0.66 g products, yield 91.7%, molecular weight 11.2 ten thousand at room temperature.
Embodiment 42
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 10 μm of ol catalyst（Aluminum complex shown in formula I, R are bromine）, 30 μm of ol benzylalcohols, 20 mL toluene and 10 mmol
Levorotatory lactide, then 90oC adds in a small amount of water and terminates reaction after reacting 2 hours, with ethanol precipitation, washing for several times, at room temperature very
Sky is dry, obtains 1.40 g products, yield 97.2%, molecular weight 7.8 ten thousand.
Embodiment 43
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
Add in 10 μm of ol catalyst（Aluminum complex shown in formula I, R are bromine）, 20 μm of ol benzylalcohols, 20 mL toluene and 15 mmol
Levorotatory lactide is subsequently placed in 110oIn the oil bath of C, reaction adds in a small amount of water and terminates reaction after 1 hour, with ethanol precipitation, wash
It washs for several times, is dried in vacuo at room temperature, obtain 2.11 g products, yield 97.7%, molecular weight 17.3 ten thousand.
Comparative example 1
The preparation of Raney nickel：Ligand structure formula such as above formula used（II）, R is bromine, and reaction process is：0.40 g of ligand is dissolved in
In 20 mL absolute ethyl alcohols, the nickel acetate of 1.0 times of ligand moles is added at room temperature, heating reflux reaction 12 hours, reaction terminates
It is concentrated in vacuo solvent later, adds in dichloromethane and solid is precipitated, filter and simultaneously washed with hexane, dry Raney nickel, structure
Formula is as follows.
Method according to embodiment 43 prepares polylactide, unlike：Catalyst used is above-mentioned Raney nickel.Instead
A small amount of water is added in after answering 24 hours and terminates reaction, with methanol extraction, washing for several times, is dried in vacuo at room temperature, obtains 0.40 g products,
18.5 % of yield, molecular weight 2.0 ten thousand.The Raney nickel is too low to the polymerization activity of lactide, is not worth.
Comparative example 2
The preparation of Al catalysts：Ligand structure formula such as following formula used（LH2）, reaction process is：In anhydrous and oxygen-free and inert gas
Under protection, 0.20 g of ligand is dissolved in 10 mL toluene, the trimethyl aluminium of 1.0 times of ligand moles is added at -5 DEG C, is delayed
Slowly it is heated to 80 DEG C after being warmed to room temperature to react 12 hours, reaction is concentrated in vacuo solvent after terminating, addition drying hexane is precipitated solid
Body is filtered and is simultaneously washed with hexane, dry Al catalysts, structural formula LAlMe as follows.
Method according to embodiment 39 prepares polylactide, unlike：Catalyst used is the Al catalysts.In nothing
It is reacted under water anaerobic and inert gas shielding, sequentially adds in 100 in the ampulla after being toasted with high pure nitrogen gas washing first
μm ol catalyst, 100 μm of ol benzylalcohols, 10 mL toluene and 10 mmol rac-lactide, then respectively 20oC and
80oIt is reacted under C, adds in a small amount of water after reaction and terminate reaction, with methanol extraction, washing for several times, be dried in vacuo at room temperature.
Wherein, it reacts at 20 DEG C 36 hours and is generated without product, illustrate that the catalyst can not be catalyzed third at a lower temperature
The polymerization of lactide.
1.15 g products, 79.9 % of yield, molecular weight 1.4 ten thousand, the selection of isotaxy solid are obtained within 24 hours in 80 DEG C of reactions
PropertyP m = 0.53.It compares with the Al catalysts of embodiment 39, stereoselectivity and activity are all than relatively low.
Comparative example 3
Method according to embodiment 35 prepares polylactide, unlike：Catalyst used is patent 201410609375.8
Catalyst used in middle embodiment 10.After reaction gained polylactide be heterotactic polylactide, quality 1.33
G, yield 92.4%, molecular weight are 1.7 ten thousand, heterotactic stereoselectivityP r It is 0.71.
Comparative example 4
Under nitrogen atmosphere, by ligand A（R is tertiary butyl）0.20 g is dissolved in 8 mL drying n-hexanes, and ligand is added at -5 DEG C
The triisopropylaluminiuand of 1.3 times of moles of A after reaction temperature is raised to room temperature naturally, is heated to 30 DEG C and reacts 24 hours, reaction
27 microlitres of water are added in afterwards and stop reaction, and organic phase is collected in liquid separation, and anhydrous sodium sulfate drying is spin-dried for solvent, and discovery obtains compound
Do not change（Isopropyl does not carry out C=O addition reactions）.Triisopropylaluminiuand can not carry out addition reaction.
Comparative example 5
Method according to embodiment 35 prepares polylactide, unlike：Catalyst used is aluminum complex, R shown in formula I
For methoxyl group.The quality of products obtained therefrom is 0.94 g after reaction 36 hours, and yield 65.3%, molecular weight is 1.1 ten thousand, Quan Tong
Vertical structure stereoselectivityP m= 0.70。
Comparative example 6
P-methyl benzenesulfonic acid is dissolved into dimethylbenzene, is first slowly added into 1, the 3- propane diamine of p-methyl benzenesulfonic acid equimolar amounts, then add
Enter the phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, heating reflux reaction, reaction is cooled to room temperature by solid after terminating
Filtering, washing, is dried to obtain solid.Solid is dissolved into dichloromethane, the saturated water of excessive sodium bicarbonate is slowly added dropwise
Solution, room temperature reaction, after reaction liquid separation are dried with anhydrous magnesium sulfate, are spin-dried for solvent, obtain unilateral phthalic anhydride and protect
1, the 3- propane diamine of shield.The propane diamine of unilateral phthalic anhydride protection and 3, the 5- Dibromosalicylaldehydes of equimolar amounts are in methyl alcohol
It is heated to reflux, reaction is put into refrigerator after terminating and cools down, and solid is precipitated, and filtering is washed with cold methanol, dry, is changed
Close object LD.
The preparation of Al catalysts：Under nitrogen atmosphere, 0.20 g of compound L D are dissolved in 10 mL dry toluenes, -10
The trimethyl aluminium of 1.0 times of compound L D moles is added at DEG C, after reaction temperature is raised to room temperature naturally, is heated to 110 DEG C instead
It answers 1 hour, vacuum drains solvent after reaction terminates, and adds in dry n-hexane washing, filtering, drying, obtains 0.18 g and consolidate
Body, yield 81.8%, the aluminium compound through hydrolysis after do mass spectral characteristi find such ligand can only unilateral generation addition reaction obtain
To LDAlMe2（HRESI-MS: m/z cacld. C18H14Br2N2O3 [M-H]-; 462.9294, found: 462.9292）.
Method according to embodiment 35 prepares polylactide, unlike：Catalyst used is the Al catalysts.Reaction
The quality of products obtained therefrom is 0.60 g afterwards, and yield 41.7%, molecular weight is 1.2 ten thousand, no stereoselectivity.
Claims (10)
1. a kind of ligand of aldehyde radical containing bigcatkin willow, it is characterized in that：Its structural formula is as shown in following formula A or II；In formula A and formula II, R is
The alkane or halogen of hydrogen, C1-C4, preferably tertiary butyl or bromine；
。
2. a kind of preparation method of the ligand of the aldehyde radical described in claim 1 containing bigcatkin willow, it is characterized in that including the following steps：
The preparation method of ligand includes the following steps shown in formula A：P-methyl benzenesulfonic acid is dissolved into dimethylbenzene, is first slowly added into pair
The ethylenediamine of toluenesulfonic acid equimolar amounts adds the phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, and then heating carries out
Back flow reaction is cooled to room temperature after reaction, filters to take solid, and obtained solid is dissolved into dichloromethane, then slowly
Saturated sodium bicarbonate aqueous solution is added dropwise to be reacted, to slough p-methyl benzenesulfonic acid, gained organic phase is used in liquid separation after reaction
Anhydrous magnesium sulfate is dried, and is then spin-dried for solvent, obtains the ethylenediamine of unilateral phthalic anhydride protection；
The ethylenediamine that unilateral phthalic anhydride is protected and the salicylide of equimolar amounts or derivatives thereof dissolve in methyl alcohol, add
Heat carries out back flow reaction, cools down, filters after reaction, obtained solid is washed with cold methanol, dried, and obtains ligand shown in formula A；Institute
The structural formula of salicylide or derivatives thereof is stated as shown in following formula B, wherein R is hydrogen, the alkane or halogen of C1-C4, preferably tertiary fourth
Base or bromine；
。
3. the preparation method of ligand includes the following steps shown in formula II：Ligand shown in formula A is added in organic solvent, -10~0oTrimethyl aluminium is added under C, reaction temperature is made to be warmed to room temperature naturally after adding, temperature is then risen to 30~110oC is reacted,
Water is added in into reaction solution after reaction, liquid separation is stood after being sufficiently mixed, collects organic phase obtained by liquid separation, recycling is organic molten
Agent obtains crude product, and crude product is recrystallized, and obtains ligand shown in formula II.
4. preparation method according to claim 2, it is characterized in that：The molar ratio 1 of ligand shown in formula A and trimethyl aluminium：1~
1.3, preferably 1：1~1.05.
5. preparation method according to claim 2, it is characterized in that：The organic solvent is dry hexane, toluene and ring
One or both of hexane；Recrystallization solvent is methanol or/and ethyl alcohol.
6. preparation method according to claim 2, it is characterized in that：Consumption of organic solvent for reaction raw materials gross mass 5~
40 times；The dosage of water is the mole of 3 times of ligand shown in formula A.
7. preparation method according to claim 2, it is characterized in that：It is raised to room temperature and temperature is risen to 30~110 again lateroC
（It is preferred that 40~60oC）Reaction 1~12 hour is preferably reacted 3~6 hours.
8. preparation method according to claim 2, it is characterized in that：Reaction carries out under gas shield.
9. the ligand of the aldehyde radical described in claim 1 containing bigcatkin willow should as the ligand of the catalyst of cyclic lactone ring-opening polymerization
With, it is preferred that the cyclic lactone is levorotatory lactide, Study of Meso-Lactide, rac-lactide, glycolide or caprolactone.
10. a kind of catalyst of cyclic lactone ring-opening polymerization, it is characterized in that：Its structural formula described in formula I, wherein, R is
The alkane or halogen of hydrogen, C1-C4, preferably tertiary butyl or bromine；
。
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| CN108239102B (en) * | 2017-12-12 | 2020-09-08 | 济南大学 | Aluminum complex containing salicylaldehyde group and preparation method and application thereof |
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