CN115806504B - Asymmetric chiral ligand and preparation method thereof, prepared catalyst, synthesis method and application thereof - Google Patents
Asymmetric chiral ligand and preparation method thereof, prepared catalyst, synthesis method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000003446 ligand Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000010949 copper Substances 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- NCNGKAPNQHDQBA-UHFFFAOYSA-N methyl 6-chloro-2-hydroxy-3-oxo-1h-indene-2-carboxylate Chemical compound ClC1=CC=C2C(=O)C(C(=O)OC)(O)CC2=C1 NCNGKAPNQHDQBA-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 96
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- 150000001879 copper Chemical class 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
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- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- RCYOYAJXIRTEDK-UHFFFAOYSA-N 3-tert-butyl-5-formyl-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C=O)=C1O RCYOYAJXIRTEDK-UHFFFAOYSA-N 0.000 claims description 5
- STVVMTBJNDTZBF-VIFPVBQESA-N L-phenylalaninol Chemical compound OC[C@@H](N)CC1=CC=CC=C1 STVVMTBJNDTZBF-VIFPVBQESA-N 0.000 claims description 5
- BYUCBODSULLYIS-UHFFFAOYSA-N methyl 6-chloro-3-oxo-1,2-dihydroindene-2-carboxylate Chemical compound ClC1=CC=C2C(=O)C(C(=O)OC)CC2=C1 BYUCBODSULLYIS-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 8
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- 239000013078 crystal Substances 0.000 description 16
- 239000012621 metal-organic framework Substances 0.000 description 10
- 239000005907 Indoxacarb Substances 0.000 description 9
- VBCVPMMZEGZULK-NRFANRHFSA-N indoxacarb Chemical compound C([C@@]1(OC2)C(=O)OC)C3=CC(Cl)=CC=C3C1=NN2C(=O)N(C(=O)OC)C1=CC=C(OC(F)(F)F)C=C1 VBCVPMMZEGZULK-NRFANRHFSA-N 0.000 description 9
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- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WXBLLCUINBKULX-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 WXBLLCUINBKULX-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
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- QMEQBOSUJUOXMX-UHFFFAOYSA-N 2h-oxadiazine Chemical group N1OC=CC=N1 QMEQBOSUJUOXMX-UHFFFAOYSA-N 0.000 description 1
- PVFDJRIEGYDIEK-UHFFFAOYSA-N 3-tert-butyl-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC=C1O PVFDJRIEGYDIEK-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 235000021513 Cinchona Nutrition 0.000 description 1
- 241000157855 Cinchona Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 101000827703 Homo sapiens Polyphosphoinositide phosphatase Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 101100109871 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) aro-8 gene Proteins 0.000 description 1
- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- HVVNJUAVDAZWCB-YFKPBYRVSA-N [(2s)-pyrrolidin-2-yl]methanol Chemical class OC[C@@H]1CCCN1 HVVNJUAVDAZWCB-YFKPBYRVSA-N 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000073 carbamate insecticide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 239000011982 enantioselective catalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- NCNGKAPNQHDQBA-NSHDSACASA-N methyl (2s)-6-chloro-2-hydroxy-3-oxo-1h-indene-2-carboxylate Chemical compound ClC1=CC=C2C(=O)[C@@](C(=O)OC)(O)CC2=C1 NCNGKAPNQHDQBA-NSHDSACASA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000012074 organic phase Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
技术领域Technical Field
本发明涉及配位化学和手性化学技术领域,具体涉及一种不对称手性配体及其制备方法、制备的催化剂、合成方法及应用。The present invention relates to the technical field of coordination chemistry and chiral chemistry, and in particular to an asymmetric chiral ligand and a preparation method thereof, a prepared catalyst, a synthesis method and application thereof.
背景技术Background technique
茚虫威(indoxacarb)是一种具有噁二嗪结构的氨基甲酸酯类杀虫剂,因其分子结构中含有一个手性碳原子,从而茚虫威有R和S两种构型的对映异构体,但是只有S-构型的茚虫威才具有杀虫活性。为高效制备有杀虫活性的茚虫威,目前采取的大多数合成路线是将5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯(简称为β-茚酮酸酯)不对称地催化转化为(2S)-5-氯-2,3-二氢-2-羟基-1-氧-1H-茚-2-羧酸甲酯(茚虫威的关键中间体),进而合成单一S-构型的茚虫威。其中不对称催化转化反应所使用的催化剂主要为金鸡纳碱衍生物、手性膦希夫碱-Cu(I)、酒石酸衍生的手性胍、手性Salen-Zr配合物、手性Zr-Salen聚合物、S-噻吗洛尔衍生物等,但这些手性催化剂存在结构不稳定、活性位点少、制备成本高等缺点,严重制约了茚虫威的合成,因此亟需研发框架结构稳定、活性位点密集、催化效果优异的异相催化剂,用于茚虫威手性关键中间体的合成。Indoxacarb is a carbamate insecticide with an oxadiazine structure. Because of its chiral carbon atom in its molecular structure, indoxacarb has two enantiomers, R and S, but only the S-configuration indoxacarb has insecticidal activity. In order to efficiently prepare insecticidal indoxacarb, most of the synthetic routes currently adopted are to asymmetrically catalytically convert 5-chloro-1-oxo-2,3-dihydroindane-2-carboxylic acid methyl ester (abbreviated as β-indanone ester) into (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indane-2-carboxylic acid methyl ester (a key intermediate of indoxacarb), and then synthesize a single S-configuration indoxacarb. The catalysts used in asymmetric catalytic transformation reactions are mainly cinchona alkaloid derivatives, chiral phosphine Schiff base-Cu(I), tartaric acid-derived chiral guanidines, chiral Salen-Zr complexes, chiral Zr-Salen polymers, S-timolol derivatives, etc., but these chiral catalysts have disadvantages such as unstable structure, few active sites and high preparation cost, which seriously restrict the synthesis of indoxacarb. Therefore, it is urgent to develop heterogeneous catalysts with stable framework structure, dense active sites and excellent catalytic effect for the synthesis of chiral key intermediates of indoxacarb.
金属-有机框架材料(MOFs)是利用功能化的有机配体与金属离子进行配位而形成的具有周期性网络结构的有机-无机杂化晶态材料,其结构和功能可以通过合理地选择和调控有机配体的结构和金属离子的种类而实现,因此这类材料成为构建具有不同结构和功能的催化剂的理想平台。特别是将手性引入到多孔的金属-有机框架中,将有助于开发具有不对称催化功能的固相手性催化剂,例如公开号为CN101830920A的中国专利申请文献中公开了一种脯氨醇衍生物诱导具有不对称催化作用的手性MOFs材料,该材料能作为非均相催化剂用于不对称硅氰化反应,因而催化剂可循环利用,产率高达100%,ee值也达到99%;公开号为CN103301885A的中国专利申请文献中公开了一种具有不对称催化作用的手性POM/MOFs的制备方法,其合成简单易操作,原料价格低廉,产率高,得到的功能材料化学性质稳定,易于大面积推广应用。MOFs催化材料比表面积大,使用量只需要底物的千分之七,就有很好的转化率和立体选择性,适合工业大规模生产之需求。尽管如此,设计与合成框架结构稳定、活性位点密集以及催化效果优异的手性多核金属-有机框架固相催化剂在当前仍然面临很大的挑战,而能成功应用于β-茚酮酸酯不对称转化为(2S)-5-氯-2,3-二氢-2-羟基-1-氧-1H-茚-2-羧酸甲酯的高效手性多核金属-有机框架催化剂则更加罕见。Metal-organic framework materials (MOFs) are organic-inorganic hybrid crystalline materials with periodic network structures formed by coordination of functionalized organic ligands and metal ions. Their structures and functions can be achieved by rationally selecting and regulating the structures of organic ligands and the types of metal ions. Therefore, such materials become an ideal platform for constructing catalysts with different structures and functions. In particular, introducing chirality into porous metal-organic frameworks will help develop solid-phase chiral catalysts with asymmetric catalytic functions. For example, a Chinese patent application document with publication number CN101830920A discloses a chiral MOFs material with asymmetric catalytic effects induced by prolinol derivatives. The material can be used as a heterogeneous catalyst for asymmetric silylation reactions, so the catalyst can be recycled, with a yield of up to 100% and an ee value of 99%. A Chinese patent application document with publication number CN103301885A discloses a method for preparing chiral POM/MOFs with asymmetric catalytic effects. The synthesis is simple and easy to operate, the raw material price is low, the yield is high, and the obtained functional material has stable chemical properties and is easy to promote and apply on a large scale. MOFs catalytic materials have a large specific surface area, and only need to use 0.7% of the substrate to achieve good conversion rate and stereoselectivity, which is suitable for large-scale industrial production. Despite this, the design and synthesis of chiral polynuclear metal-organic framework solid-phase catalysts with stable framework structure, dense active sites and excellent catalytic effect still face great challenges at present, and efficient chiral polynuclear metal-organic framework catalysts that can be successfully used for the asymmetric conversion of β-indanone ester to (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester are even rarer.
发明内容Summary of the invention
本发明所要解决的技术问题在于提供一种全新的不对称手性配体,并提供一种结构稳定、活性位点密集以及在高对映选择性催化β-茚酮酸酯转化为S构型5-氯-2,3-二氢-2-羟基-1-氧-1H-茚-2-羧酸甲酯的过程中催化效果优异的全新的手性多核铜金属-有机框架催化剂。The technical problem to be solved by the present invention is to provide a new asymmetric chiral ligand, and to provide a new chiral multinuclear copper metal-organic framework catalyst with a stable structure, dense active sites and excellent catalytic effect in the process of highly enantioselectively catalyzing the conversion of β-indanone ester into S-configuration 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester.
本发明通过以下技术手段实现解决上述技术问题:The present invention solves the above technical problems through the following technical means:
一种不对称手性配体,其结构式如下:An asymmetric chiral ligand, the structural formula of which is as follows:
本发明还提出一种所述的不对称手性配体的制备方法,包括以下步骤:将3-叔丁基-5-醛基-4-羟基苯甲酸和L-苯丙氨醇溶于甲醇中,回流反应,反应结束后趁热过滤得到所述不对称手性配体。The present invention also provides a method for preparing the asymmetric chiral ligand, comprising the following steps: dissolving 3-tert-butyl-5-aldehyde-4-hydroxybenzoic acid and L-phenylalaninol in methanol, refluxing the mixture, and filtering the mixture while hot after the reaction is completed to obtain the asymmetric chiral ligand.
优选地,所述3-叔丁基-5-醛基-4-羟基苯甲酸的化学结构式为:其制备可以按照文献J.Am.Chem.Soc.,2010.132(43):15390-15398所述方法,具体包括以下步骤:Preferably, the chemical structural formula of the 3-tert-butyl-5-formyl-4-hydroxybenzoic acid is: The preparation method can be based on the method described in J.Am.Chem.Soc., 2010.132(43):15390-15398, which specifically includes the following steps:
将4-羟基-3-叔丁基苯甲酸(1.55g,7.95mmol)与六亚甲基四胺(2.23g,15.9mmol)一起装入250mL圆底烧瓶中,然后加入三氟乙酸(63mL)并将溶液加热回流18小时。然后将50mL质量分数为33%的H2SO4添加到反应中,并将溶液再回流3小时。反应结束后,混合溶液用乙醚稀释并用水、盐水洗涤,然后有机相通过硫酸镁干燥,真空浓缩得到1.2克3-叔丁基-5-醛基-4-羟基苯甲酸。4-Hydroxy-3-tert-butylbenzoic acid (1.55 g, 7.95 mmol) and hexamethylenetetramine (2.23 g, 15.9 mmol) were placed in a 250 mL round bottom flask, and trifluoroacetic acid (63 mL) was added and the solution was heated to reflux for 18 hours. Then 50 mL of 33% H 2 SO 4 was added to the reaction, and the solution was refluxed for another 3 hours. After the reaction was completed, the mixed solution was diluted with ether and washed with water and brine, and then the organic phase was dried over magnesium sulfate and concentrated in vacuo to obtain 1.2 g of 3-tert-butyl-5-formyl-4-hydroxybenzoic acid.
优选地,所述3-叔丁基-5-醛基-4-羟基苯甲酸、L-苯丙氨醇的摩尔比为1:1.2~1.5。Preferably, the molar ratio of 3-tert-butyl-5-formyl-4-hydroxybenzoic acid to L-phenylalaninol is 1:1.2-1.5.
优选地,所述回流反应的时间为5~10h。Preferably, the reflux reaction time is 5 to 10 hours.
本发明还提出一种手性多核铜金属-有机框架催化剂,采用所述的不对称手性配体为配体制备而成,其化学式为Cu3L2,其中L的结构式如下所示:The present invention also provides a chiral multinuclear copper metal-organic framework catalyst, which is prepared using the asymmetric chiral ligand as a ligand, and has a chemical formula of Cu 3 L 2 , wherein the structural formula of L is as follows:
所述手性多核铜金属-有机框架催化剂的晶胞参数如下:空间群为P32,α=β=90°,γ=120°,Z=3。The unit cell parameters of the chiral multi-nuclear copper metal-organic framework catalyst are as follows: the space group is P3 2 , α=β=90°,γ=120°, Z=3.
本发明采用一种具有三齿螯合位点的不对称的希夫碱手性配体H3L(即(S,E)-3-(叔丁基)-4-羟基-5-((1-羟基-3-苯丙烷-2-基)亚氨基)甲基)苯甲酸)作为桥联单元,来构建具有三核铜结构的手性金属-有机框架催化剂;所述配体H3L由3-叔丁基-5-醛基-4-羟基苯甲酸和L-苯丙氨醇在甲醇中回流反应得到;所述手性多核铜金属-有机框架催化剂单晶结构中手性配体与金属铜离子的连接方式如下;The present invention adopts an asymmetric Schiff base chiral ligand H 3 L (i.e. (S, E)-3-(tert-butyl)-4-hydroxy-5-((1-hydroxy-3-phenylpropane-2-yl)imino)methyl)benzoic acid) with a tridentate chelating site as a bridging unit to construct a chiral metal-organic framework catalyst with a trinuclear copper structure; the ligand H 3 L is obtained by reflux reaction of 3-tert-butyl-5-aldehyde-4-hydroxybenzoic acid and L-phenylalaninol in methanol; the connection mode between the chiral ligand and the metal copper ion in the single crystal structure of the chiral multinuclear copper metal-organic framework catalyst is as follows;
其中,n为任一整数; Wherein, n is any integer;
有益效果:本发明的手性多核铜金属-有机框架催化剂,其骨架是由具有4-连接作用的三核Cu3O8N2簇与周围的4个手性不对称希夫碱相互连接而成。该催化剂结构具有一个1.03nm疏水性手性孔道,其中周期性地镶嵌了配位不饱和的金属铜位点,可以作为潜在的可循环使用的固相手性催化剂。Beneficial effects: The chiral multinuclear copper metal-organic framework catalyst of the present invention has a framework composed of a trinuclear Cu 3 O 8 N 2 cluster with a 4-connection effect and four surrounding chiral asymmetric Schiff bases connected to each other. The catalyst structure has a 1.03nm hydrophobic chiral pore in which unsaturated metal copper sites are periodically embedded, and can be used as a potential recyclable solid-phase chiral catalyst.
本发明还提出一种所述的手性多核铜金属-有机框架催化剂的合成方法,其以铜盐为金属盐,以所述不对称手性配体为有机桥联配体,以N,N’-二甲基甲酰胺与甲醇为溶剂进行配位反应,反应结束后冷却至室温,再将反应产物置于冰水浴中冷却得到所述手性多核铜金属-有机框架催化剂。The present invention also proposes a method for synthesizing the chiral multi-nuclear copper metal-organic framework catalyst, which uses copper salt as the metal salt, the asymmetric chiral ligand as the organic bridging ligand, and N,N'-dimethylformamide and methanol as solvents for coordination reaction. After the reaction is completed, the reaction is cooled to room temperature, and the reaction product is placed in an ice water bath for cooling to obtain the chiral multi-nuclear copper metal-organic framework catalyst.
有益效果:本发明制备手性多核铜金属-有机框架催化剂采用二次冷却结晶法,方法简单、反应省时,可大量制备。Beneficial effects: The invention prepares the chiral multi-nuclear copper metal-organic framework catalyst by a secondary cooling crystallization method, which is simple, time-saving and can be prepared in large quantities.
优选地,所述的手性多核铜金属-有机框架催化剂的合成方法,包括以下步骤:Preferably, the method for synthesizing the chiral multi-nuclear copper metal-organic framework catalyst comprises the following steps:
S1、将铜盐、N,N’-二甲基甲酰胺与甲醇混合,然后滴加至所述不对称手性配体的甲醇溶液中,加热搅拌后除去蓝色浑浊物,取蓝色澄清液;S1. Mix copper salt, N,N'-dimethylformamide and methanol, and then add dropwise to the methanol solution of the asymmetric chiral ligand, remove the blue turbidity after heating and stirring, and take a blue clear liquid;
S2、将S1中的蓝色澄清液密封于带聚四氟乙烯内衬的高压反应釜中进行溶剂热反应,反应结束后冷却至室温,将反应产物再置于冰水浴中冷却得到所述手性多核铜金属-有机框架催化剂。S2. The blue clear liquid in S1 is sealed in a high-pressure reactor with a polytetrafluoroethylene liner to carry out a solvothermal reaction. After the reaction is completed, the reaction product is cooled to room temperature and then placed in an ice water bath to cool to obtain the chiral multi-nuclear copper metal-organic framework catalyst.
优选地,所述不对称手性配体与铜盐的摩尔比为1:1.5-3;N,N’-二甲基甲酰胺、溶解铜盐的甲醇、溶解不对称手性配体的甲醇的体积比为1:1-3:1-3;所述溶剂热反应的温度为90-110℃,时间为1-2.5h。Preferably, the molar ratio of the asymmetric chiral ligand to the copper salt is 1:1.5-3; the volume ratio of N,N'-dimethylformamide, methanol for dissolving the copper salt, and methanol for dissolving the asymmetric chiral ligand is 1:1-3:1-3; the temperature of the solvent thermal reaction is 90-110°C, and the time is 1-2.5h.
优选地,所述不对称手性配体与铜盐的摩尔比为1:2;所述溶剂热反应的温度为100℃,时间为1h。Preferably, the molar ratio of the asymmetric chiral ligand to the copper salt is 1:2; the temperature of the solvent thermal reaction is 100° C. and the time is 1 hour.
优选地,N,N’-二甲基甲酰胺、溶解铜盐的甲醇、溶解不对称手性配体的甲醇的体积比为1:2:1。Preferably, the volume ratio of N,N'-dimethylformamide, methanol for dissolving the copper salt, and methanol for dissolving the asymmetric chiral ligand is 1:2:1.
优选地,所述铜盐为Cu(OAc)2·H2O、Cu(ClO4)2·6H2O、Cu(NO3)2·3H2O、CuCl2·2H2O中的一种或多种的混合物。Preferably, the copper salt is a mixture of one or more of Cu(OAc) 2 ·H 2 O, Cu(ClO 4 ) 2 ·6H 2 O, Cu(NO 3 ) 2 ·3H 2 O, and CuCl 2 ·2H 2 O.
优选地,所述铜盐为Cu(OAc)2·H2O。Preferably, the copper salt is Cu(OAc) 2 ·H 2 O.
优选地,在S1中,加热至35-45℃搅拌25-35min后除去蓝色浑浊物。Preferably, in S1, the blue turbidity is removed after heating to 35-45°C and stirring for 25-35 minutes.
优选地,在S1中,加热至40℃搅拌30min后除去蓝色浑浊物。Preferably, in S1, the blue turbidity is removed after heating to 40°C and stirring for 30 minutes.
本发明还提出一种所述手性多核铜金属-有机框架催化剂在不对称催化氧化5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯制备S-构型5-氯-2,3-二氢-2-羟基-1-氧-1H-茚-2-羧酸甲酯中的应用。The present invention also proposes an application of the chiral multi-nuclear copper metal-organic framework catalyst in the asymmetric catalytic oxidation of 5-chloro-1-oxo-2,3-dihydroindene-2-carboxylic acid methyl ester to prepare S-configuration 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester.
优选地,所用氧化剂为异丙苯过氧化氢;所用溶剂为甲苯;反应的温度为室温。Preferably, the oxidant used is cumene hydroperoxide; the solvent used is toluene; and the reaction temperature is room temperature.
优选地,所用氧化剂和反应底物5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯的物质的量之比为1.3-1.7:1;所述手性多核铜金属-有机框架催化剂与反应底物5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯的质量比为1:25。Preferably, the molar ratio of the oxidant used and the reaction substrate 5-chloro-1-oxo-2,3-dihydroindane-2-carboxylic acid methyl ester is 1.3-1.7:1; the mass ratio of the chiral multi-nuclear copper metal-organic framework catalyst to the reaction substrate 5-chloro-1-oxo-2,3-dihydroindane-2-carboxylic acid methyl ester is 1:25.
优选地,所用氧化剂和反应底物5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯的物质的量之比为1.5:1。Preferably, the molar ratio of the oxidant to the reaction substrate 5-chloro-1-oxo-2,3-dihydroindane-2-carboxylic acid methyl ester is 1.5:1.
有益效果:氧化剂的量是反应底物5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯的1.5倍比较合适,降低了氧化剂产率有所降低,超过1.5倍,产率没有明显变化。Beneficial effect: The amount of the oxidant is 1.5 times that of the reaction substrate 5-chloro-1-oxo-2,3-dihydroindane-2-carboxylic acid methyl ester, which is more appropriate. The yield is reduced when the oxidant is reduced, and there is no obvious change in the yield when it exceeds 1.5 times.
有益效果:本发明中的手性多核铜金属-有机框架催化剂能够以99.7%的对映选择性和93%的产率催化氧化5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯制备S-构型5-氯-2,3-二氢-2-羟基-1-氧-1H-茚-2-羧酸甲酯,且催化剂可循环使用多次而不失活性。Beneficial effects: The chiral multinuclear copper metal-organic framework catalyst of the present invention can catalyze the oxidation of 5-chloro-1-oxo-2,3-dihydroindene-2-carboxylic acid methyl ester with 99.7% enantioselectivity and 93% yield to prepare S-configuration 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester, and the catalyst can be recycled for multiple times without losing activity.
本发明所述手性多核铜金属-有机框架催化剂是以Cu为金属中心与手性配体H3L通过二次冷却结晶而成的有纳米疏水性手性孔道的三维结构晶体,其分子式为Cu3L2,其中手性配体H3L为(S,E)-3-(叔丁基)-4-羟基-5-((1-羟基-3-苯丙烷-2-基)亚氨基)甲基)苯甲酸;H3L的结构式为The chiral multi-nuclear copper metal-organic framework catalyst of the present invention is a three-dimensional structure crystal with nano hydrophobic chiral channels formed by secondary cooling crystallization with Cu as the metal center and chiral ligand H 3 L, and its molecular formula is Cu 3 L 2 , wherein the chiral ligand H 3 L is (S, E)-3-(tert-butyl)-4-hydroxy-5-((1-hydroxy-3-phenylpropane-2-yl)imino)methyl)benzoic acid; the structural formula of H 3 L is
本发明的优点在于:本发明的手性多核铜金属-有机框架催化剂是采用二次冷却结晶法来制备的,简单省时且能大量制备;催化剂结构具有尺寸为1.03nm的疏水性手性孔道,并高密度地镶嵌了催化活性的金属铜位点,从而能够简单而高效地催化氧化β-茚酮酸酯而制备单一构型的茚虫威的关键中间体S-构型-5-氯-2,3-二氢-2-羟基-1-氧-1H-茚-2-羧酸甲酯,且催化剂可以多次循环使用。The invention has the advantages that the chiral multi-nuclear copper metal-organic framework catalyst is prepared by a secondary cooling crystallization method, which is simple, time-saving and can be prepared in large quantities; the catalyst structure has a hydrophobic chiral pore with a size of 1.03 nm, and is densely inlaid with catalytically active metal copper sites, so that β-indanone esters can be simply and efficiently catalytically oxidized to prepare the key intermediate S-configuration-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester of a single configuration of indoxacarb, and the catalyst can be recycled for multiple times.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明实施例1中制备的不对称手性配体H3L的核磁谱图;FIG1 is a nuclear magnetic resonance spectrum of the asymmetric chiral ligand H 3 L prepared in Example 1 of the present invention;
图2为本发明实施例1制备的手性多核铜金属-有机框架催化剂中铜离子的配位与连接方式图;FIG2 is a diagram showing the coordination and connection mode of copper ions in the chiral multi-nuclear copper metal-organic framework catalyst prepared in Example 1 of the present invention;
图3为本发明实施例1制备的手性多核铜金属-有机框架催化剂的三维多孔结构图;FIG3 is a three-dimensional porous structure diagram of the chiral multi-nuclear copper metal-organic framework catalyst prepared in Example 1 of the present invention;
图4为本发明实施例1中手性多核铜金属-有机框架催化剂及手性配体H3L的红外光谱图;FIG4 is an infrared spectrum of the chiral multinuclear copper metal-organic framework catalyst and the chiral ligand H 3 L in Example 1 of the present invention;
图5为本发明实施例4中催化反应产物的核磁共振氢谱图;FIG5 is a hydrogen nuclear magnetic resonance spectrum of the catalytic reaction product in Example 4 of the present invention;
图6为本发明实施例4中催化反应产物的高效液相谱图。FIG6 is a high performance liquid chromatography spectrum of the catalytic reaction product in Example 4 of the present invention.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
下述实施例中所用的试验材料和试剂等,如无特殊说明,均可从商业途径获得。Unless otherwise specified, the test materials and reagents used in the following examples can be obtained from commercial sources.
实施例中未注明具体技术或条件者,均可以按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。If no specific techniques or conditions are specified in the examples, they can be carried out according to the techniques or conditions described in the literature in the art or according to the product instructions.
实施例1Example 1
不对称手性配体H3L的合成,具体步骤如下:将3-叔丁基-5-醛基-4-羟基苯甲酸(2.2g,10mmol)和L-苯丙氨醇(1.8g,12mmol)溶于30mL甲醇中,回流反应5小时,趁热过滤得到黄色固体即为不对称手性配体H3L,产率80%;对制备的不对称手性配体H3L的核磁进行测试,其核磁谱图如图1所示,1H NMR(600MHz,DMSO-d6)δ12.43(s,1H,COOH),8.40(s,1H,NCH),7.87–7.73(m,2H,2×ArH),7.29–7.07(m,5H,5×ArH),5.03(s,1H,ArOH),3.90(d,J=5.7Hz,1H,CH2OH),3.67–3.60(m,2H,CH2OH),3.52–3.48(m,1H,NCH),3.01–2.84(m,2H,ArCH2),1.35(s,9H,C(CH3)3)。The synthesis of the asymmetric chiral ligand H 3 L is as follows: 3-tert-butyl-5-formyl-4-hydroxybenzoic acid (2.2 g, 10 mmol) and L-phenylalaninol (1.8 g, 12 mmol) are dissolved in 30 mL of methanol, refluxed for 5 hours, and filtered while hot to obtain a yellow solid, namely the asymmetric chiral ligand H 3 L, with a yield of 80%. The prepared asymmetric chiral ligand H 3 L is tested by nuclear magnetic resonance, and its nuclear magnetic spectrum is shown in Figure 1. 1 H NMR (600 MHz, DMSO-d 6 )δ12.43(s,1H,COOH),8.40(s,1H,NCH ),7.87–7.73(m,2H,2×ArH ),7.29–7.07(m,5H,5×ArH ),5.03(s,1H,ArOH),3.90(d,J=5.7Hz,1H,CH 2 OH), 3.67–3.60 (m, 2H, CH 2 OH), 3.52–3.48 (m, 1H, NCH), 3.01–2.84 (m, 2H, ArCH 2 ), 1.35 (s, 9H, C(CH 3 ) 3 ).
一种手性多核铜金属-有机框架催化剂的合成方法,具体包括以下步骤:A method for synthesizing a chiral multi-nuclear copper metal-organic framework catalyst specifically comprises the following steps:
(1)将Cu(OAc)2·H2O(399mg,2.0mmol)溶于10mL DMF和20mL甲醇(MeOH)的混合液中,滴加至不对称手性配体H3L(355mg,1.0mmol)的MeOH(10mL)溶液中,40℃条件加热搅拌30分钟后,过滤除去蓝色浑浊物,并将蓝色澄清液密封于100mL带聚四氟乙烯内衬的高压反应釜中。(1) Cu(OAc) 2 · H2O (399 mg, 2.0 mmol) was dissolved in a mixture of 10 mL DMF and 20 mL methanol (MeOH), and added dropwise to a solution of asymmetric chiral ligand H3L (355 mg, 1.0 mmol) in MeOH (10 mL). After heating and stirring at 40°C for 30 min, the blue turbidity was removed by filtration, and the blue clear liquid was sealed in a 100 mL polytetrafluoroethylene-lined autoclave.
(2)在100℃的高温恒温烘箱中加热反应釜,持续1小时,以确保金属盐和手性配体充分反应。(2) The reactor was heated in a high temperature constant temperature oven at 100° C. for 1 hour to ensure that the metal salt and the chiral ligand were fully reacted.
(3)停止加热、冷却至室温,随后将高压反应釜中蓝色溶液置于冰水浴中,得到蓝色米粒状晶体,过滤,洗涤,风干,即可得到所述的手性多核铜金属-有机框架催化剂,产率为60%。(3) stopping heating and cooling to room temperature, then placing the blue solution in the autoclave in an ice-water bath to obtain blue rice-like crystals, filtering, washing, and air-drying to obtain the chiral multi-nuclear copper metal-organic framework catalyst with a yield of 60%.
对实施例1中得到的手性多核铜金属-有机框架催化剂的晶体结构进行测定。The crystal structure of the chiral multi-nuclear copper metal-organic framework catalyst obtained in Example 1 was determined.
测定方法:采用上海光源同步辐射技术,对尺寸合适的本发明单晶样品进行数据收集,利用APEX3软件对获得衍射数据进行还原,利用SHELXS-2014程序对晶体结构进行解析及精修,其间通过全矩阵最小二乘法(full-matrix least-squares refinement basedon F2)定出所有非氢原子并完成原子的各向异性精修,而不对称手性配体骨架上的氢原子则通过理论加氢完成。Determination method: Shanghai Light Source synchrotron radiation technology is used to collect data on single crystal samples of the present invention of suitable size, APEX3 software is used to restore the obtained diffraction data, and the crystal structure is analyzed and refined using the SHELXS-2014 program. During this process, all non-hydrogen atoms are determined by the full-matrix least-squares refinement based on F2 and the anisotropic refinement of atoms is completed, while the hydrogen atoms on the asymmetric chiral ligand skeleton are completed by theoretical hydrogenation.
测定结果:本发明的手性多核铜金属-有机框架催化剂单晶的晶胞参数如下:空间群为P32,α=β=90°,γ=120°,Z=3。Measurement results: The unit cell parameters of the chiral multi-nuclear copper metal-organic framework catalyst single crystal of the present invention are as follows: the space group is P3 2 , α=β=90°,γ=120°, Z=3.
通过对本发明的手性多核铜金属-有机框架催化剂的单晶数据进行解析,可知其结晶于三方晶系的手性P32空间群,其不对称单元包含2个晶相独立的金属配体CuL单元和一个Cu(II)离子。如图2所示,两个晶相独立的金属配体CuL单元与这一Cu(II)离子在另外两个CuL配体末端羧基的桥联作用下,形成一个Cu3O8N2的三核铜金属簇。三核铜簇中2个金属配体CuL中的Cu(II)离子采取四配位的扭曲平面结构,而另外1个Cu(II)离子采取四配位的扭曲四面体结构。该三核铜簇可作为4-连接的节点与周围的4个配体相连接,形成一个三维结构的手性金属-有机框架,沿c-轴具有1个尺寸为1.03nm的手性通道,手性通道中不但布满了叔丁基和苯环等疏水性基团,而且高密度地镶嵌了配位不饱和的金属铜离子,如图3所示,这类结构类似于金属酶的手性口袋,因而可以作为一种潜在不对称催化剂。此外通过对比手性配体和手性多核铜金属-有机框架催化剂的红外谱图(如图4所示),可以发现手性多核铜金属-有机框架催化剂在1675cm-1处的手性配体羧基的特征振动峰消失,可以证明金属铜离子与配体发生了配位,这与单晶结构分析结果是一致的。By analyzing the single crystal data of the chiral multi-nuclear copper metal-organic framework catalyst of the present invention, it can be known that it crystallizes in the chiral P3 2 space group of the trigonal system, and its asymmetric unit contains two crystal-phase independent metal ligand CuL units and a Cu(II) ion. As shown in Figure 2, the two crystal-phase independent metal ligand CuL units and the Cu(II) ion form a Cu 3 O 8 N 2 trinuclear copper metal cluster under the bridging effect of the terminal carboxyl groups of the other two CuL ligands. The Cu(II) ions in the two metal ligands CuL in the trinuclear copper cluster adopt a four-coordinated distorted planar structure, while the other one Cu(II) ion adopts a four-coordinated distorted tetrahedral structure. The trinuclear copper cluster can be connected to the surrounding four ligands as a 4-connected node to form a three-dimensional chiral metal-organic framework with a chiral channel of 1.03nm along the c-axis. The chiral channel is not only filled with hydrophobic groups such as tert-butyl and benzene rings, but also densely inlaid with unsaturated metal copper ions, as shown in Figure 3. This type of structure is similar to the chiral pocket of metal enzymes, and can be used as a potential asymmetric catalyst. In addition, by comparing the infrared spectra of chiral ligands and chiral multinuclear copper metal-organic framework catalysts (as shown in Figure 4), it can be found that the characteristic vibration peak of the chiral ligand carboxyl group of the chiral multinuclear copper metal-organic framework catalyst at 1675cm -1 disappears, which can prove that the metal copper ions are coordinated with the ligands, which is consistent with the results of single crystal structure analysis.
实施例2Example 2
一种手性多核铜金属-有机框架催化剂的合成方法,具体包括以下步骤:A method for synthesizing a chiral multi-nuclear copper metal-organic framework catalyst specifically comprises the following steps:
(1)将Cu(OAc)2·H2O(1.5mmol)溶于10mL DMF和10mL MeOH的混合溶液中,滴加至不对称手性配体H3L(355mg,1.0mmol)的MeOH(10mL)溶液中,35℃条件加热搅拌25分钟后,过滤除去蓝色浑浊物,并将蓝色澄清液密封于100mL带聚四氟乙烯内衬的高压反应釜中。(1) Cu(OAc) 2 ·H 2 O (1.5 mmol) was dissolved in a mixed solution of 10 mL DMF and 10 mL MeOH, and added dropwise to a solution of asymmetric chiral ligand H 3 L (355 mg, 1.0 mmol) in MeOH (10 mL). After heating and stirring at 35° C. for 25 min, the blue turbidity was removed by filtration, and the blue clear liquid was sealed in a 100 mL polytetrafluoroethylene-lined autoclave.
(2)在110℃的高温恒温烘箱中加热反应釜,持续1.5小时,以确保金属盐和手性配体充分反应。(2) The reactor was heated in a high temperature constant temperature oven at 110° C. for 1.5 hours to ensure that the metal salt and the chiral ligand were fully reacted.
(3)停止加热、冷却至室温,随后将高压反应釜中蓝色溶液置于冰水浴中,得到蓝色米粒状晶体,过滤,洗涤,风干,即可得到所述的手性多核铜金属-有机框架催化剂。(3) stopping heating and cooling to room temperature, then placing the blue solution in the autoclave in an ice water bath to obtain blue rice-like crystals, filtering, washing, and air-drying to obtain the chiral multi-nuclear copper metal-organic framework catalyst.
实施例3Example 3
一种手性多核铜金属-有机框架催化剂的合成方法,具体包括以下步骤:A method for synthesizing a chiral multi-nuclear copper metal-organic framework catalyst specifically comprises the following steps:
(1)将Cu(OAc)2·H2O(3.0mmol)溶于10mL DMF和30mL MeOH的混合溶液中,滴加至不对称手性配体H3L(355mg,1.0mmol)的MeOH(30mL)溶液中,45℃条件加热搅拌25分钟后,过滤除去蓝色浑浊物,并将蓝色澄清液密封于100mL带聚四氟乙烯内衬的高压反应釜中。(1) Cu(OAc) 2 ·H 2 O (3.0 mmol) was dissolved in a mixed solution of 10 mL DMF and 30 mL MeOH, and added dropwise to a solution of asymmetric chiral ligand H 3 L (355 mg, 1.0 mmol) in MeOH (30 mL). After heating and stirring at 45° C. for 25 min, the blue turbidity was removed by filtration, and the blue clear liquid was sealed in a 100 mL polytetrafluoroethylene-lined autoclave.
(2)在90℃的高温恒温烘箱中加热反应釜,持续2小时,以确保金属盐和手性配体充分反应。(2) The reaction vessel was heated in a high temperature constant temperature oven at 90° C. for 2 hours to ensure that the metal salt and the chiral ligand were fully reacted.
(3)停止加热、冷却至室温,随后将高压反应釜中蓝色溶液置于冰水浴中,得到蓝色米粒状晶体,过滤,洗涤,风干,即可得到所述的手性多核铜金属-有机框架催化剂。(3) stopping heating and cooling to room temperature, then placing the blue solution in the autoclave in an ice water bath to obtain blue rice-like crystals, filtering, washing, and air-drying to obtain the chiral multi-nuclear copper metal-organic framework catalyst.
实施例4Example 4
一种手性多核铜金属-有机框架催化剂的合成方法,具体包括以下步骤:A method for synthesizing a chiral multi-nuclear copper metal-organic framework catalyst specifically comprises the following steps:
(1)将Cu(OAc)2·H2O(3.0mmol)溶于10mL DMF和15mL MeOH的混合溶液中,滴加至不对称手性配体H3L(355mg,1.0mmol)的MeOH(20mL)溶液中,40℃条件加热搅拌35分钟后,过滤除去蓝色浑浊物,并将蓝色澄清液密封于100mL带聚四氟乙烯内衬的高压反应釜中。(1) Cu(OAc) 2 ·H 2 O (3.0 mmol) was dissolved in a mixed solution of 10 mL DMF and 15 mL MeOH, and added dropwise to a solution of asymmetric chiral ligand H 3 L (355 mg, 1.0 mmol) in MeOH (20 mL). After heating and stirring at 40° C. for 35 min, the blue turbidity was removed by filtration, and the blue clear liquid was sealed in a 100 mL polytetrafluoroethylene-lined autoclave.
(2)在105℃的高温恒温烘箱中加热反应釜,持续2.5小时,以确保金属盐和手性配体充分反应。(2) The reactor was heated in a high temperature constant temperature oven at 105° C. for 2.5 hours to ensure that the metal salt and the chiral ligand were fully reacted.
(3)停止加热、冷却至室温,随后将高压反应釜中蓝色溶液置于冰水浴中,得到蓝色米粒状晶体,过滤,洗涤,风干,即可得到所述的手性多核铜金属-有机框架催化剂。(3) stopping heating and cooling to room temperature, then placing the blue solution in the autoclave in an ice water bath to obtain blue rice-like crystals, filtering, washing, and air-drying to obtain the chiral multi-nuclear copper metal-organic framework catalyst.
实施例5Example 5
一种手性多核铜金属-有机框架催化剂的合成方法,具体包括以下步骤:A method for synthesizing a chiral multi-nuclear copper metal-organic framework catalyst specifically comprises the following steps:
将Cu(ClO4)2·6H2O(2.0mmol)溶于10mL DMF和30mL MeOH的混合溶液中,滴加至不对称手性配体H3L(355mg,1.0mmol)的MeOH(30mL)溶液中,45℃条件加热搅拌25分钟后,过滤除去蓝色浑浊物,并将蓝色澄清液密封于100mL带聚四氟乙烯内衬的高压反应釜中,在90℃的高温恒温烘箱中加热反应釜,持续反应2小时。停止加热、冷却至室温,随后将高压反应釜中蓝色溶液置于冰水浴中,得到蓝色米粒状晶体,过滤,洗涤,风干,即可得到所述的手性多核铜金属-有机框架催化剂。Cu(ClO 4 ) 2 ·6H 2 O (2.0 mmol) was dissolved in a mixed solution of 10 mL DMF and 30 mL MeOH, and then added dropwise to a solution of asymmetric chiral ligand H 3 L (355 mg, 1.0 mmol) in MeOH (30 mL). After heating and stirring at 45° C. for 25 minutes, the blue turbidity was removed by filtration, and the blue clear liquid was sealed in a 100 mL autoclave with a polytetrafluoroethylene liner, and the autoclave was heated in a high temperature constant temperature oven at 90° C. for 2 hours. The heating was stopped, cooled to room temperature, and then the blue solution in the autoclave was placed in an ice water bath to obtain blue rice-like crystals, which were filtered, washed, and air-dried to obtain the chiral multi-nuclear copper metal-organic framework catalyst.
实施例6Example 6
一种手性多核铜金属-有机框架催化剂的合成方法,具体包括以下步骤:A method for synthesizing a chiral multi-nuclear copper metal-organic framework catalyst specifically comprises the following steps:
将Cu(NO3)2·3H2O(2.0mmol)溶于10mL DMF和30mL MeOH的混合溶液中,滴加至不对称手性配体H3L(355mg,1.0mmol)的MeOH(30mL)溶液中,45℃条件加热搅拌25分钟后,过滤除去蓝色浑浊物,并将蓝色澄清液密封于100mL带聚四氟乙烯内衬的高压反应釜中,在90℃的高温恒温烘箱中加热反应釜,持续反应2小时。停止加热、冷却至室温,随后将高压反应釜中蓝色溶液置于冰水浴中,得到蓝色米粒状晶体,过滤,洗涤,风干,即可得到所述的手性多核铜金属-有机框架催化剂。Cu(NO 3 ) 2 ·3H 2 O (2.0 mmol) was dissolved in a mixed solution of 10 mL DMF and 30 mL MeOH, and then added dropwise to a MeOH (30 mL) solution of asymmetric chiral ligand H 3 L (355 mg, 1.0 mmol), heated and stirred at 45° C. for 25 minutes, filtered to remove blue turbidity, and sealed the blue clear liquid in a 100 mL polytetrafluoroethylene-lined autoclave, heated the autoclave in a high-temperature constant temperature oven at 90° C., and continued to react for 2 hours. Heating was stopped, cooled to room temperature, and then the blue solution in the autoclave was placed in an ice-water bath to obtain blue rice-like crystals, which were filtered, washed, and air-dried to obtain the chiral multi-nuclear copper metal-organic framework catalyst.
实施例7Example 7
一种手性多核铜金属-有机框架催化剂的合成方法,具体包括以下步骤:A method for synthesizing a chiral multi-nuclear copper metal-organic framework catalyst specifically comprises the following steps:
将CuCl2·2H2O(2.0mmol)溶于10mL DMF和30mL MeOH的混合溶液中,滴加至不对称手性配体H3L(355mg,1.0mmol)的MeOH(30mL)溶液中,45℃条件加热搅拌25分钟后,过滤除去蓝色浑浊物,并将蓝色澄清液密封于100mL带聚四氟乙烯内衬的高压反应釜中,在90℃的高温恒温烘箱中加热反应釜,持续反应2小时。停止加热、冷却至室温,随后将高压反应釜中蓝色溶液置于冰水浴中,得到蓝色米粒状晶体,过滤,洗涤,风干,即可得到所述的手性多核铜金属-有机框架催化剂。CuCl 2 ·2H 2 O (2.0 mmol) was dissolved in a mixed solution of 10 mL DMF and 30 mL MeOH, and then added dropwise to a solution of asymmetric chiral ligand H 3 L (355 mg, 1.0 mmol) in MeOH (30 mL). After heating and stirring at 45° C. for 25 minutes, the blue turbidity was removed by filtration, and the blue clear solution was sealed in a 100 mL autoclave with a polytetrafluoroethylene liner, and the autoclave was heated in a high-temperature constant temperature oven at 90° C. for 2 hours. The heating was stopped, the autoclave was cooled to room temperature, and then the blue solution in the autoclave was placed in an ice water bath to obtain blue rice-like crystals, which were filtered, washed, and air-dried to obtain the chiral multi-nuclear copper metal-organic framework catalyst.
对比例1Comparative Example 1
当利用二甲亚砜(DMSO)代替实施例1中的DMF,利用四氢呋喃代替实施例1中的甲醇,而保持其他条件和操作过程与实施例1一致,未能得到蓝色米粒状的目标手性多核铜金属-有机框架催化剂晶体。When dimethyl sulfoxide (DMSO) was used instead of DMF in Example 1, and tetrahydrofuran was used instead of methanol in Example 1, while other conditions and operation procedures were kept consistent with Example 1, blue rice-shaped target chiral multi-nuclear copper metal-organic framework catalyst crystals could not be obtained.
实施例8Example 8
不对称催化氧化5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯转化为S-构型的5-氯-2,3-二氢-2-羟基-1-氧-1H-茚-2-羧酸甲酯实验,其路线如下:The asymmetric catalytic oxidation of 5-chloro-1-oxo-2,3-dihydroindene-2-carboxylic acid methyl ester into S-configuration 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester was carried out. The route is as follows:
鉴于手性多核铜金属-有机框架催化剂中存在开放的疏水性手性纳米孔道和丰富的催化活性位点,我们检验了其不对称催化氧化β-茚酮酸酯5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯的能力。具体实验过程如下:将2.24克(10mmol)5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯、25mL甲苯、90毫克本发明实施例1制备的手性多核铜金属-有机框架催化剂搅拌混合30分钟,然后将2.28克(15mmol)的异丙苯过氧化氢(CHP)加入至上述混合反应液中,室温反应3小时,过滤回收催化剂,滤液浓缩后经硅胶色谱柱分离得到2.23克白色固体,即目标产物S-构型的5-氯-2,3-二氢-2-羟基-1-氧-1H-茚-2-羧酸甲酯(产率为93%,核磁如图5所示)。经高效液相色谱分析,高效液相谱图如图6所示,其光学纯度为99.7%。将过滤回收后的手性多核铜金属-有机框架催化剂经无水丙酮洗涤后自然风干后,可以继续催化该反应,结果显示第五次催化反应后的产率依然高达90%,产物的光学纯度仍然能得以保持。In view of the presence of open hydrophobic chiral nanopores and abundant catalytic active sites in the chiral multi-nuclear copper metal-organic framework catalyst, we examined its ability to asymmetric catalytic oxidation of β-indanone ester 5-chloro-1-oxo-2,3-dihydroindane-2-carboxylic acid methyl ester. The specific experimental process is as follows: 2.24 grams (10 mmol) of 5-chloro-1-oxo-2,3-dihydroindane-2-carboxylic acid methyl ester, 25 mL of toluene, and 90 mg of the chiral multi-nuclear copper metal-organic framework catalyst prepared in Example 1 of the present invention were stirred and mixed for 30 minutes, and then 2.28 grams (15 mmol) of isopropylbenzene hydroperoxide (CHP) was added to the above mixed reaction solution, reacted at room temperature for 3 hours, filtered to recover the catalyst, and the filtrate was concentrated and separated by silica gel chromatography to obtain 2.23 grams of white solid, i.e., the target product S-configuration 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indane-2-carboxylic acid methyl ester (yield 93%, NMR as shown in Figure 5). After high performance liquid chromatography analysis, the high performance liquid chromatography spectrum is shown in Figure 6, and its optical purity is 99.7%. After the chiral multi-nuclear copper metal-organic framework catalyst is filtered and recovered, it is washed with anhydrous acetone and naturally air-dried, and then the reaction can be continued to be catalyzed. The results show that the yield after the fifth catalytic reaction is still as high as 90%, and the optical purity of the product can still be maintained.
实施例9Example 9
与实施例8的不同在于:具体实验过程中,异丙苯过氧化氢为13mmol;本发明的手性多核铜金属-有机框架催化剂为90毫克时,目标产物的产率降低到85%左右。The difference from Example 8 is that in the specific experimental process, the amount of cumene hydroperoxide is 13 mmol; when the amount of the chiral multi-nuclear copper metal-organic framework catalyst of the present invention is 90 mg, the yield of the target product is reduced to about 85%.
实施例10Example 10
与实施例8的不同在于:具体实验过程中,异丙苯过氧化氢为17mmol;本发明的手性多核铜金属-有机框架催化剂为90毫克时,目标产物的产率保持在93%左右,没有明显增加。The difference from Example 8 is that in the specific experimental process, the amount of isopropylbenzene hydroperoxide is 17 mmol; when the amount of the chiral multi-nuclear copper metal-organic framework catalyst of the present invention is 90 mg, the yield of the target product is maintained at about 93%, without a significant increase.
对比例2Comparative Example 2
与实施例8的不同为:具体实验过程中,将氧化剂更换为相同物质量的双氧水时,而其它反应条件保持不变,该催化氧化反应几乎得不到高光学纯度的目标产物。The difference from Example 8 is that during the specific experiment, when the oxidant is replaced with hydrogen peroxide of the same amount, while other reaction conditions remain unchanged, the catalytic oxidation reaction can hardly obtain the target product with high optical purity.
对比例3Comparative Example 3
当调整氧化剂CHP和反应底物5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯的物质的量为1:1时,催化反应产率明显降低。具体实施方案如下,将2.24克(10mmol)5-氯-1-氧代-2,3-二氢茚-2-羧酸甲酯、25mL甲苯、90毫克本发明实施例1的手性多核铜金属-有机框架催化剂搅拌混合30分钟,然后将1.52克(10mmol)的CHP滴加至上述混合反应液中,室温反应3小时,过滤回收催化剂,滤液浓缩后经硅胶色谱柱分离得到1.80克目标产物,产率约为75%。When the amount of the oxidant CHP and the reaction substrate 5-chloro-1-oxo-2,3-dihydroindane-2-carboxylic acid methyl ester is adjusted to 1:1, the catalytic reaction yield is significantly reduced. The specific implementation scheme is as follows: 2.24 grams (10 mmol) of 5-chloro-1-oxo-2,3-dihydroindane-2-carboxylic acid methyl ester, 25 mL of toluene, and 90 mg of the chiral multi-nuclear copper metal-organic framework catalyst of Example 1 of the present invention are stirred and mixed for 30 minutes, and then 1.52 grams (10 mmol) of CHP is added dropwise to the above mixed reaction liquid, reacted at room temperature for 3 hours, filtered to recover the catalyst, and the filtrate is concentrated and separated by silica gel chromatography to obtain 1.80 grams of the target product, with a yield of about 75%.
以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.
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