CN114656494A - Method for preparing allyl borate by using modified chitosan copper material - Google Patents
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 97
- -1 allyl borate Chemical compound 0.000 title claims abstract description 95
- 239000000463 material Substances 0.000 title claims abstract description 92
- 239000010949 copper Substances 0.000 title claims abstract description 82
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000002262 Schiff base Substances 0.000 claims description 57
- 150000004753 Schiff bases Chemical class 0.000 claims description 57
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 20
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 17
- 239000012074 organic phase Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 229910001431 copper ion Inorganic materials 0.000 claims description 15
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000007832 Na2SO4 Substances 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- CDXSJGDDABYYJV-UHFFFAOYSA-N acetic acid;ethanol Chemical compound CCO.CC(O)=O CDXSJGDDABYYJV-UHFFFAOYSA-N 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- ILEIUTCVWLYZOM-UHFFFAOYSA-N 2-hydroxy-5-methylbenzaldehyde Chemical compound CC1=CC=C(O)C(C=O)=C1 ILEIUTCVWLYZOM-UHFFFAOYSA-N 0.000 claims description 5
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 4
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052796 boron Inorganic materials 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000007259 addition reaction Methods 0.000 abstract description 4
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 abstract description 4
- 235000019441 ethanol Nutrition 0.000 description 31
- 238000001228 spectrum Methods 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 150000001299 aldehydes Chemical group 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 125000000879 imine group Chemical group 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical group OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 125000000746 allylic group Chemical group 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- HCEAAUGYFOIOEH-UHFFFAOYSA-N methyl 2-[hydroxy-(4-methylphenyl)methyl]prop-2-enoate Chemical compound COC(=O)C(=C)C(O)C1=CC=C(C)C=C1 HCEAAUGYFOIOEH-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical compound OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VZGOKIHNKHAORQ-UHFFFAOYSA-N methyl 2-[hydroxy(phenyl)methyl]prop-2-enoate Chemical compound COC(=O)C(=C)C(O)C1=CC=CC=C1 VZGOKIHNKHAORQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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- 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
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing allyl borate by using a modified chitosan copper material, which specifically comprises the following steps: 1) adding an MBH alcohol compound I, pinacol diboron and a catalytic material Schiff-CS @ Cu into a solvent formed by mixing methanol and water, and mixing and stirring at room temperature for reacting for 6-24 hours; 2) and after the reaction is finished, filtering, purifying the filtrate to obtain allyl borate II, washing and drying the precipitate to obtain the recovered catalytic material Schiff-CS @ Cu, and recycling for the next time. The Schiff-CS @ Cu catalytic material has high catalytic activity, can be applied to catalyzing boron addition reaction of various MBH alcohols, takes a mixed solution of methanol and water as a solvent, is carried out at room temperature, and is simple, convenient and easy to operate; the method has the advantages of mild reaction conditions, small catalyst consumption, high product yield and the like; the catalytic material can be recycled for many times, is environment-friendly and has wide industrial application prospect.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for preparing allyl borate by using a modified chitosan copper material.
Background
Allylic metal reagents have received much attention in recent years due to the efficient construction of C — C bonds in cross-coupling reactions and allylic reactions, and among these allylic metal reagents, allylborate salts have received much attention due to its low toxicity and excellent stability, ease of handling and ease of availability. MBH alcohols have both allyl and α, β -unsaturated carbonyl moieties and are widely used as synthons in organic synthesis. However, there are few reports on direct boriding reactions of MBH alcohols due to poor leaving ability of the carbonyl group. In 2004, the use of CuCl, a monovalent copper salt, and Pd (OAc), a palladium salt, were reported in the literature (J.org.chem.,2004,69,5807.) and the literature (org.Lett.,2004,6,481.) respectively2The MBH ester is catalyzed to carry out the boronization reaction to obtain the allyl borate, but the reaction is accompanied with the problems of strong alkali use, high temperature, high cost, environmental pollution, incapability of recycling the catalyst and the like. In 2017, the literature (Organic Chemistry frontiers, 2017,4.) for the first time achieved the conversion of MBH alcohols to allylborate, which work used 1.2 equivalents of B2(pin)210 mol% of lithium tert-butoxide added as a base, 10 mol% of Cu (OTf)2Adding tertiary butanol as a catalyst, reacting at room temperature for 12h to obtain the allyl borate with higher yield, adding a large amount of alkali in the reaction process to pollute the environment although the reaction achieves the high-efficiency conversion of MBH alcohol to the allyl borate, and simultaneously using a large amount of Cu (OTf) as the catalyst2High cost. Although the method improves the reaction activity, the method also has the problems of limited reaction conditions, high cost, environmental pollution, incapability of recycling the catalyst and the like, and the application of the method in actual production is greatly limited. Therefore, it is urgent to develop a new green and environment-friendly method for directly converting MBH alcohol into allyl borate with high yield, which is simple and easy to operate, mild in conditions, and low in cost.
Chitosan is the only alkaline polysaccharide in the nature, has no pollution to the environment, has the characteristics of good degradability, biocompatibility, antibacterial property and the like, but has the defects of easy swelling, poor mechanical strength and the like. The chitosan Schiff base material obtained by modifying chitosan with aldehyde compounds not only retains the characteristics of good degradability, biocompatibility, antibacterial property and the like of chitosan, but also improves the physicochemical property of chitosan and improves the stability of chitosan. The structure of the chitosan Schiff base material contains a large amount of hydroxyl and imine groups, and the chitosan Schiff base material is easy to coordinate with transition metal and is widely applied in the field of catalysis. The chitosan Schiff base catalytic material obtained by modifying chitosan to adsorb transition metal by using aldehyde compounds is reported to realize the construction of C-C bonds and C-N bonds, but the reports on the construction of C-B bonds of the material are less so far.
Disclosure of Invention
The invention aims to solve the defects of the background technology, provides a method for preparing allyl borate by using a modified chitosan copper material, and aims to overcome the problems of large catalyst consumption, high cost, incapability of recycling, difficulty in industrialization, addition of alkali and the like in the prior art to a certain extent.
The technical scheme of the invention is as follows: a method for preparing allyl borate by using a modified chitosan copper material is characterized by comprising the following steps:
1) adding an MBH alcohol compound I, diboronic acid pinacol ester and a chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu into a solvent formed by mixing methanol and water, mixing and stirring at room temperature for 6-24 h, wherein the mass ratio of the MBH alcohol compound I: pinacol ester diborate: the copper content of the chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu is 1 (1.2-2): 0.005-0.03, the volume ratio of methanol to water in a solvent is (0.25-4): 1, and the chemical reaction equation is as follows:
wherein R is1Is phenyl, p-methylphenyl, p-methoxyphenyl, p-tert-butylphenyl, p-fluorophenyl or p-chlorophenyl;
2) and after the reaction is finished, filtering, separating and purifying the obtained filtrate to obtain allyl borate II, washing and drying the precipitate to obtain the recovered chitosan Schiff base copper functional material Schiff-CS @ Cu, and recycling the next step.
Preferably, the copper content in the chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu in the step 1) is 0.5-1.4 mmol/g.
Preferably, the MBH alcohol compound I in step 1): pinacol ester diborate: the amount ratio of copper substances in the chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu is 1:2: 0.01.
Preferably, the dosage ratio of the Schiff-CS @ Cu supported copper catalytic material Schiff-CS @ Cu supported copper of the chitosan Schiff base in the step 1) to the solvent is 0.001-0.006 mmol:2 ml.
Preferably, the reaction is carried out for 12h at room temperature with mixing and stirring in step 1).
Preferably, the separation and purification of the filtrate obtained in step 2) to obtain allyl borate II specifically comprises: extracting the filtrate with ethyl acetate to obtain organic phase containing product, and passing through anhydrous Na2SO4Drying, filtering and rotary evaporating to remove the redundant organic solvent, and purifying the obtained residual organic phase by using a mixed solvent column chromatography of ethyl acetate and petroleum ether to obtain the allyl borate II.
Preferably, the chitosan Schiff base supported copper catalytic material Schiff-CS @ Cu in the step 1) is prepared by a method comprising the following steps:
a. adding chitosan and aldehyde compound into the ethanol-acetic acid mixed solution, stirring and reacting for 12-24 h at 65-75 ℃, wherein the aldehyde compound is 5-methylOne of salicylaldehyde, salicylaldehyde and 5-nitro salicylaldehyde, aldehyde group-CHO in aldehyde compound and amino group-NH in chitosan2The molar ratio is 2-6: 1, and after the reaction is finished, chitosan Schiff base powder is obtained through separation treatment;
b. putting chitosan Schiff base powder into a divalent copper ion solution, stirring for 3-9 h at 50-75 ℃ for divalent copper ion adsorption, and after adsorption, separating to obtain the chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu.
Further, in the step a, the ethanol-acetic acid mixed solution is obtained by mixing glacial acetic acid and absolute ethyl alcohol according to the volume ratio of 1: 7-8, and aldehyde-CHO in aldehyde compounds and amino-NH in chitosan2The molar ratio was 4: 1. The acetic acid of the invention adopts the glacial acetic acid which is sold in the market, namely, the mixed solution of anhydrous acetic acid and ethanol acetic acid as the solvent.
Further, Cu contained in the divalent copper ion solution in the step b2+With amino-NH in chitosan2The molar ratio is at least 1:1, and the concentration of copper ions in the divalent copper ion solution is 0.1-0.5 mol/L. The divalent copper ion solution is a copper sulfate solution and is used for providing sufficient copper ions for the chitosan Schiff base material, so that the copper ion adsorption is realized through the self-adsorption capacity of the chitosan Schiff base material.
Further, the separation processes in steps a and b each include: filtering, washing with anhydrous ethanol and distilled water repeatedly and alternately, and oven drying at 50 deg.C for 12 hr.
The invention uses chitosan Schiff base powder to prepare allyl borate by using a copper-supported catalytic material. The unique compatibility and spatial structure of the chitosan Schiff base powder supported copper catalytic material are utilized, the complexation is stronger, and the catalytic activity is higher; in addition, the chitosan Schiff base material contains a large amount of imine groups and unreacted amino groups, so that an alkaline environment is provided for the reaction without adding any alkali; meanwhile, the catalyst can be recycled for a plurality of times, accords with the concept of green chemistry, and has industrial application prospect.
The invention has the beneficial effects that:
1. the chitosan Schiff base powder has good biocompatibility, is green and environment-friendly, has good effect of immobilizing metal copper, has longer service life, can be conveniently separated from other components in a reaction system by a solid-liquid phase separation method after the reaction of the chitosan Schiff base powder immobilized copper catalytic material is finished, and can be recycled by simple regeneration, thereby reducing the production cost and obviously reducing various environmental pollution problems.
2. The method has mild reaction conditions, does not need to add any alkali, carries out reaction at room temperature, and is simple, convenient and easy to operate.
3. The method can realize higher conversion rate of reactants only by using lower catalyst dosage.
4. The method has wide applicability, can be used for boron addition of various MBH alcohols of different types, and successfully prepares the corresponding allyl borate.
5. Chitosan schiff base material to Cu2+The adsorption of (2) is mainly performed by imine group coordination, and the main reaction comprises:
schiff reaction: r' -NH2+RCHO→R′-N＝CHR (1)
Coordination:
after the chitosan is modified by the aldehyde compound, the coordination capability is changed, the catalytic activity of the catalyst is improved, and primary amine (R' -NH) on the chitosan2) Reacting with aldehydes (RHC ═ O) by Schiff base to obtain imine (R) containing carbon-nitrogen double bond2C ═ NR' -), Schiff base reaction reduces the amino group on the surface of chitosan, but N atom in C ═ N double bond formed by Schiff base reaction and O atom in adjacent OH are easy to react with Cu due to the rich hydroxyl group on the surface of chitosan2+The complexing takes place to form a conjugate plane, and the complexing effect on copper ions is stronger through chemical adsorption.
6. When chitosan is modified with an aldehyde compound, acetalization occurs, and-C ═ O of the aldehyde compound is substituted for-NH of the chitosan unit2In large excess, sufficient imine groups are formed for the formation of stable complexes with copper ions. But too much excess is caused by the aldolizationThe O atom in OH adjacent to the N atom in the C ═ N double bond decreases, decreasing the reactant yield, so when Schiff-CS @ Cu is prepared as chitosan Schiff base powder, C ═ O in aldehyde and-NH of chitosan2A molar ratio of 4:1 is preferred.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a target product in example 4;
FIG. 2 is the nuclear magnetic carbon spectrum of the target product in example 4.
Detailed Description
The following specific examples further illustrate the invention in detail. The drugs used in the examples are commercially available products unless otherwise specified, and the methods used are conventional in the art without further specification.
Example 1
The embodiment provides a method for obtaining Schiff-CS @ Cu catalytic material L1 by modifying chitosan with 5-methyl salicylaldehyde, which comprises the following specific preparation processes:
a. preparing chitosan schiff base powder: chitosan powder (1.0g) and 5-methyl salicylaldehyde (3.4g) were added to 85mL of an ethanol-acetic acid mixed solution (obtained by mixing 75mL of absolute ethanol and 10mL of glacial acetic acid), and stirred at 65 ℃ for reaction for 12 hours. Filtering and recovering the precipitate, repeatedly and alternately washing the precipitate by using absolute ethyl alcohol and distilled water to remove unreacted 5-methyl salicylaldehyde, and drying in an oven at 50 ℃ for 12 hours to obtain chitosan Schiff base powder. The molecular formula of the chitosan is (C)6H11NO4) N, 1.0g of chitosan contained about 6.2mmol-NH2In this example, the aldehyde is used in the amount of aldehyde-CHO and amino-NH-in chitosan2The molar ratio was determined to be 4: 1. 5-methyl salicylaldehyde and-NH in chitosan2Schiff reaction takes place, consuming-NH of chitosan2Generating imine group, changing the coordination ability to metal and improving the catalytic performance.
b. Adding the chitosan Schiff base powder obtained in the step a into 30mL of copper sulfate solution (prepared from 1.6g of blue vitriol, containing 6.4mmol of Cu)2+) Stirring at 50 deg.C for 6h, filtering to separate Cu load2+The powder of (A) is washed repeatedly and alternately with absolute ethanol and distilled water to remove impuritiesThe free copper and sulfate ions were finally oven dried at 50 ℃ for 12h to yield the Schiff-CS @ Cu catalytic material designated L1.
The relative content of copper as an active ingredient in L1 was 1.36mmol/g as determined by ICP.
Example 2
The embodiment provides a method for obtaining a Schiff-CS @ Cu catalytic material L2 by modifying chitosan with salicylaldehyde, and the specific preparation process is as follows:
a. preparing chitosan schiff base powder: chitosan powder (1.0g) and salicylaldehyde (3.0g) were added to 85mL of an ethanol-acetic acid mixed solution (obtained by mixing 75mL of absolute ethanol and 10mL of glacial acetic acid), and reacted at 75 ℃ for 18 hours with stirring. Filtering and recovering precipitate, repeatedly and alternately washing the precipitate with absolute ethyl alcohol and distilled water to remove unreacted salicylaldehyde, and drying in a 50 ℃ oven for 12h to obtain chitosan Schiff base powder. The molecular formula of the chitosan is (C)6H11NO4) N, 1.0g of chitosan contained about 6.2mmol-NH2In this example, the aldehyde is used in the amount of aldehyde-CHO and amino-NH-in chitosan2The molar ratio was determined to be 4: 1.
b. Adding the chitosan Schiff base powder obtained in the step a into 30mL of copper sulfate solution (prepared from 1.6g of blue vitriol, containing 6.4mmol of Cu)2+) Stirring at 50 deg.C for 6h, filtering to separate Cu load2+Repeatedly washed alternately with absolute ethanol and distilled water to remove free copper and sulphate ions and finally oven dried at 50 ℃ for 12h to give the Schiff-CS @ Cu catalytic material designated L2.
The relative content of copper as an active ingredient in L2 was detected by ICP to be 0.877 mmol/g.
Example 3
The embodiment provides a method for obtaining Schiff-CS @ Cu catalytic material L3 by modifying chitosan with 5-nitro salicylaldehyde, and the specific preparation process is as follows:
a. preparing chitosan schiff base powder: chitosan powder (1.0g) and 5-nitro salicylaldehyde (4.1g) were added to 85mL of an ethanol-acetic acid mixed solution (obtained by mixing 75mL of absolute ethanol and 10mL of glacial acetic acid), and the mixture was stirred at 75 ℃ to react for 24 hours. FiltrationAnd (3) recovering the precipitate, repeatedly and alternately washing the precipitate by using absolute ethyl alcohol and distilled water to remove unreacted 5-nitro salicylaldehyde, and drying in an oven at 50 ℃ for 12 hours to obtain chitosan Schiff base powder. The molecular formula of the chitosan is (C)6H11NO4) N, 1.0g Chitosan approximately contains 6.2mmol-NH2In this example, the amount of aldehyde was determined in such a manner that the molar ratio of aldehyde groups-CHO contained to amino groups-NH 2 in chitosan was 4: 1.
b. Adding the chitosan Schiff base powder obtained in the step a into 30mL of copper sulfate solution (prepared from 1.6g of blue vitriol, containing 6.4mmol of Cu)2+) Stirring at 50 deg.C for 6h, filtering to separate Cu load2+Repeatedly washed alternately with absolute ethanol and distilled water to remove free copper and sulphate ions and finally oven dried at 50 ℃ for 12h to give the Schiff-CS @ Cu catalytic material designated L3.
The relative content of copper as an active ingredient in L3 was 0.528mmol/g as determined by ICP.
Comparative example
The embodiment provides a method for preparing a chitosan-supported copper CS @ Cu catalytic material L4, which comprises the following specific steps:
chitosan powder (1.0g) was added to 30mL of a copper sulfate solution (prepared from 1.6g of copper sulfate pentahydrate, containing 6.4mmol of Cu2+) Stirring at 50 deg.C for 6h, filtering to separate Cu load2+Repeatedly washed alternately with absolute ethanol and distilled water to remove free copper and sulfate ions and finally oven dried at 50 ℃ for 12h to give the CS @ Cu catalytic material designated L4.
The relative content of copper, an active ingredient, in L4, was detected to be 1.75mmol/g by ICP.
Example 4
The embodiment provides a method for preparing allyl borate by catalyzing a chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu, which comprises the following specific steps:
1) the MBH alcohol compound I, pinacol diboron ester and Schiff-CS @ Cu catalytic material L3 (prepared in example 3) were added to 2ml of a solvent (obtained by mixing methanol and water in a volume ratio of 4: 1), wherein the MBH alcohol compound I was 0.20mmol, and the pinacol diboron ester was 0.40mmol of catalytic material L3 containing 0.002mmol of copper, and reacting at room temperature for 12h under stirring, wherein the MBH alcohol compound I in this example is 2- (hydroxy (phenyl) methyl) acrylate, wherein R is1Is phenyl, and has the following reaction formula;
2) after the reaction is finished, filtering, repeatedly and alternately washing and drying the precipitate by using water and ethanol, recovering the chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu for recycling, extracting the filtrate by using ethyl acetate (3X 10mL) to obtain an organic phase containing a product, and passing the organic phase through anhydrous Na2SO4Drying, filtering and rotary evaporating to remove the redundant organic solvent. The remaining organic phase was purified by column chromatography using ethyl acetate/petroleum ether mixed solvent ═ 1:20 to give allylborate II (R)1Is phenyl). The product yield was 88% (53.2 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows, and the spectra are shown in figures 1 and 2.
1H NMR(400MHz,Chloroform-d)；δ＝7.67(s,1H),7.38–7.36(m,5H),3.80(s,3H),2.14(s,2H),1.23(s,12H).
13C NMR(100MHz,Chloroform-d)；δ＝169.1,137.6,136.2,130.1,129.4,128.3,128.0,83.5,52.1,24.7.
Example 4 shows that under the catalysis conditions of the Schiff-CS @ Cu catalytic material L3 provided in this example, the conversion rate of methyl 2- (hydroxy (phenyl) methyl) acrylate is high, and the yield of boron addition product reaches 88%.
The catalytic material L1 obtained in example 1 was applied to the boron addition reaction of methyl 2- (hydroxy (phenyl) meth) acrylate and pinacol diboron according to the above reaction procedure, with a yield of 57%.
The catalytic material L2 obtained in example 2 was applied to the boron addition reaction of methyl 2- (hydroxy (phenyl) meth) acrylate and pinacol diboron according to the above reaction procedure, with a yield of 72%.
The catalytic material L4 obtained in comparative example was applied to the boron addition reaction of methyl 2- (hydroxy (phenyl) meth) acrylate and pinacol diboron according to the above reaction procedure, with a yield of 61%.
Compared with a control group catalytic material L4, the catalytic activity of the catalytic material L3 is improved, and the stronger the electron withdrawing capability of the substituent at the 5-position of the benzene ring of the salicylaldehyde compound is, the better the catalytic effect is. The aldehyde group of the salicylaldehyde compound is positioned at the No. 2 position of a benzene ring and is a meta-position group of a No. 5 position substituent, the stronger the electron-withdrawing ability, the more obvious the activation of the meta-position substituent by the group with stronger electron-withdrawing ability is, the easier the reaction is, the more imine groups obtained by the reaction are, and the better the catalytic effect is.
Example 5
The embodiment provides a method for preparing allyl borate by catalyzing a chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu, which comprises the following specific steps:
1) MBH alcohol compound I, pinacol diborate and Schiff-CS @ Cu catalytic material L3 (prepared in example 3), wherein 0.20mmol of MBH alcohol compound I, 0.40mmol of pinacol diborate and 0.002mmol of copper in catalytic material L3 are mixed and stirred at room temperature for 12h, are added into 2ml of solvent (obtained by mixing methanol and water in a volume ratio of 4: 1), and the MBH alcohol compound I is methyl 2- (hydroxy (p-tolyl) methyl) acrylate, wherein R is1Is p-tolyl, and has the following reaction formula;
2) filtering after reaction, washing precipitate with water and ethanol repeatedly and alternately, drying, recovering copper functional material of chitosan Schiff base for recycling, extracting filtrate with ethyl acetate (3 × 10mL) to obtain organic phase containing product, and passing through anhydrous Na2SO4Drying, filtering and rotary evaporating to remove the redundant organic solvent. The remaining organic phase was purified by column chromatography using ethyl acetate/petroleum ether mixed solvent ═ 1:20 to give allylborate II (R)1P-tolyl). The product yield was 88% (55.6 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.65(s,1H),7.30–7.28(m,2H),7.19–7.16(m,2H),3.79(s,3H),2.76(s,3H),2.14(s,2H),1.23(s,12H).
13C NMR(100MHz,Chloroform-d)；δ＝169.4,138.2,137.8,133.4,129.5,129.3,129.1,83.5,52.1,24.8,21.4.
example 5 shows that under the catalysis conditions of the Schiff-CS @ Cu catalytic material L3 provided by the embodiment of the invention, the conversion rate of methyl 2- (hydroxy (p-tolyl) methyl) acrylate is high, and the yield of boron addition product reaches 88%.
Example 6
The embodiment provides a method for preparing allyl borate by catalyzing a chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu, which comprises the following specific steps:
1) adding an MBH alcohol compound I, pinacol diborate and Schiff-CS @ Cu catalytic material L3 (prepared in example 3) into 2ml of a solvent (obtained by mixing methanol and water in a volume ratio of 4: 1), wherein the MBH alcohol compound I is 0.20mmol, the pinacol diborate is 0.40mmol, and the catalytic material L3 contains 0.002mmol of copper, and carrying out mixing and stirring reaction at room temperature for 12h, wherein the MBH alcohol compound I is methyl 2- (hydroxy (p-methoxyphenyl) methyl) acrylate, R1Is p-methoxyphenyl, and the reaction formula is as follows;
2) filtering after reaction, washing precipitate with water and ethanol repeatedly and alternately, drying, recovering copper functional material of chitosan Schiff base for recycling, extracting filtrate with ethyl acetate (3 × 10mL) to obtain organic phase containing product, and passing through anhydrous Na2SO4Drying, filtering again, and rotary evaporating to remove excessive organic solvent. The remaining organic phase was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether at a ratio of 1:20 to give allyl borate II (R1 is p-methoxyphenyl). The product yield was 79% (52.5 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product, namely the allyl borate II, are shown as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.62(s,1H),7.37–7.35(m,2H),6.91–6.88(m,2H),3.82(s,3H),3.78(s,3H),2.15(s,2H),1.23(s,12H).
13C NMR(100MHz,Chloroform-d)；δ＝169.4,159.4,137.4,131.1,128.7,128.1,113.8,83.4,55.3,52.0,24.7.
example 6 shows that under the catalysis conditions of the Schiff-CS @ Cu catalytic material L3 provided by the embodiment of the invention, the conversion rate of methyl 2- (hydroxy (p-methoxyphenyl) methyl) acrylate is high, and the yield of boron addition products reaches 79%.
Example 7
The embodiment provides a method for preparing allyl borate by catalyzing a chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu, which comprises the following specific steps:
1) MBH alcohol compound I, pinacol diborate and Schiff-CS @ Cu catalytic material L3 (prepared in example 3), wherein 0.20mmol of MBH alcohol compound I, 0.40mmol of pinacol diborate and 0.002mmol of copper in catalytic material L3 are mixed and stirred at room temperature for 12h, are added into 2ml of solvent (obtained by mixing methanol and water in a volume ratio of 4: 1), and the MBH alcohol compound I is methyl 2- (hydroxy (p-tert-butylphenyl) methacrylate, wherein R is1Is p-tert-butylphenyl with the following reaction formula;
2) filtering after reaction, washing precipitate with water and ethanol repeatedly and alternately, drying, recovering chitosan Schiff base copper functional material for recycling, extracting filtrate with ethyl acetate (3 × 10mL) to obtain organic phase containing product, and passing through anhydrous Na2SO4Drying, filtering and rotary evaporating to remove the redundant organic solvent. The remaining organic phase was purified by column chromatography using ethyl acetate/petroleum ether mixed solvent ═ 1:20 to give allylborate II (R)1P-tert-butylphenyl). The product yield was 72% (51.2 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product, namely the allyl borate II, are shown as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.65(s,1H),7.40–7.33(m,4H),3.79(s,3H),2.17(s,2H),1.32(s,9H),1.22(s,12H).
13C NMR(100MHz,Chloroform-d)；δ＝169.3,151.2,137.6,133.3,129.4,129.3,125.3,83.4,52.0,34.7,31.2,24.7.
example 7 shows that under the catalysis conditions of the Schiff-CS @ Cu catalytic material L3 provided by the embodiment of the invention, the conversion rate of methyl 2- (hydroxy (p-tert-butylphenyl) methyl) acrylate is high, and the yield of boron addition products reaches 72%.
Example 8
The embodiment provides a method for preparing allyl borate by catalyzing a chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu, which comprises the following specific steps:
1) adding 0.20mmol of MBH alcohol compound I, 0.40mmol of pinacol diborate and 0.002mmol of copper in catalytic material L3 into 2ml of solvent (prepared by mixing methanol and water in a volume ratio of 4: 1) prepared in example 3, wherein the MBH alcohol compound I is methyl 2- (hydroxy (p-fluorophenyl) methyl) acrylate, R1 is p-fluorophenyl, and Schiff-CS @ Cu catalytic material L3 (prepared in example 3), and reacting for 12h at room temperature with mixing and stirring;
2) filtering after reaction, washing precipitate with water and ethanol repeatedly and alternately, drying, recovering copper functional material of chitosan Schiff base for recycling, extracting filtrate with ethyl acetate (3 × 10mL) to obtain organic phase containing product, and passing through anhydrous Na2SO4Drying, filtering and rotary evaporating to remove the redundant organic solvent. The remaining organic phase was purified by column chromatography using ethyl acetate/petroleum ether mixed solvent ═ 1:20 to give allylborate II (R)1P-fluorophenyl). The product yield was 82% (52.5 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product, namely the allyl borate II, are shown as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.62(s,1H),7.38–7.35(m,2H),7.08–7.03(m,2H),3.79(s,3H),2.10(s,2H),1.23(s,12H).
13C NMR(100MHz,Chloroform-d)；δ＝169.1,163.7,161.2,136.6,132.3,131.3,131.2,130.1,115.6,83.6,52.2,24.8.
example 8 shows that under the catalysis conditions of the Schiff-CS @ Cu catalytic material L3 provided by the embodiment of the invention, the conversion rate of methyl 2- (hydroxy (p-fluorophenyl) methyl) acrylate is high, and the yield of boron addition products reaches 82%.
Example 9
The embodiment provides a method for preparing allyl borate by catalyzing a chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu, which comprises the following specific steps:
1) the MBH alcohol compound I, pinacol diborate and Schiff-CS @ Cu catalytic material L3 (prepared in example 3), wherein 0.20mmol of the MBH alcohol compound I, 0.40mmol of pinacol diborate and 0.002mmol of copper in the catalytic material L3 are mixed and stirred at room temperature for 12h, and the Schiff-CS @ Cu catalytic material L3 (prepared in example 3) is added into 2ml of solvent (obtained by mixing methanol and water in a volume ratio of 4: 1), wherein R is methyl 2- (hydroxy (p-chlorophenyl) methyl) acrylate1Is p-chlorophenyl, and has the following reaction formula;
2) filtering after reaction, washing precipitate with water and ethanol repeatedly and alternately, drying, recovering copper functional material of chitosan Schiff base for recycling, extracting filtrate with ethyl acetate (3 × 10mL) to obtain organic phase containing product, and passing through anhydrous Na2SO4Drying, filtering and rotary evaporating to remove the redundant organic solvent. The remaining organic phase was purified by column chromatography using a mixed solvent of ethyl acetate/petroleum ether at a ratio of 1:20 to give allyl borate II (R1 is p-chlorophenyl). The product yield was 83% (55.9 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown below.
1H NMR(400MHz,Chloroform-d)；δ＝7.60(s,1H),7.33–7.32(m,4H),3.80(s,3H),2.10(s,2H),1.24(s,12H).
13C NMR(100MHz,Chloroform-d)；δ＝169.0,136.4,134.7,134.0,130.9,130.7,128.7,83.7,52.2,24.8.
Example 9 shows that under the catalysis conditions of the Schiff-CS @ Cu catalytic material L3 provided by the embodiment of the invention, the conversion rate of methyl 2- (hydroxy (p-chlorophenyl) methyl) acrylate is high, and the yield of boron addition products reaches 83%.
Claims (10)
1. A method for preparing allyl borate by using a modified chitosan copper material is characterized by comprising the following steps:
1) adding an MBH alcohol compound I, pinacol diborate and a chitosan Schiff base supported copper catalytic material Schiff-CS @ Cu into a solvent formed by mixing methanol and water, and mixing and stirring at room temperature for 6-24 h, wherein the mass ratio of the MBH alcohol compound I: pinacol ester diborate: the copper content of the chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu is 1 (1.2-2): 0.005-0.03, the volume ratio of methanol to water in a solvent is (0.25-4): 1, and the chemical reaction equation is as follows:
wherein R is1Is phenyl, p-methylphenyl, p-methoxyphenyl, p-tert-butylphenyl, p-fluorophenyl or p-chlorophenyl;
2) and after the reaction is finished, filtering, separating and purifying the obtained filtrate to obtain allyl borate II, washing and drying the precipitate to obtain the recovered chitosan Schiff base copper functional material Schiff-CS @ Cu, and performing next-step recycling.
2. The method for preparing allyl borate by using the modified chitosan copper catalytic material as claimed in claim 1, wherein the copper content in the chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu in step 1) is 0.5-1.4 mmol/g.
3. The method for preparing allyl borate using a modified chitosan copper material according to claim 1, wherein the MBH alcohol compound I in step 1): pinacol ester diboron: the amount ratio of copper substances in the chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu is 1:2: 0.01.
4. The method for preparing allyl borate by using the modified chitosan copper material as claimed in claim 1, wherein the ratio of the amount of the chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu supported copper to the solvent in step 1) is 0.001-0.006 mmol:2 ml.
5. The method for preparing allyl borate using modified chitosan copper material as claimed in claim 1, wherein the step 1) is performed by mixing and stirring at room temperature for 12 h.
6. The method for preparing allyl borate using modified chitosan copper material as claimed in claim 1, wherein the filtrate obtained in step 2) is separated and purified to obtain allyl borate II, which specifically comprises: the filtrate was extracted with ethyl acetate to give an organic phase containing the product, which was passed over anhydrous Na2SO4Drying, filtering and rotary evaporating to remove the redundant organic solvent, and purifying the obtained residual organic phase by using a mixed solvent column chromatography of ethyl acetate and petroleum ether to obtain the allyl borate II.
7. The method for preparing allyl borate by using the modified chitosan copper material as claimed in claim 1, wherein the chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu in the step 1) is prepared by a method comprising the following steps:
a. adding chitosan and an aldehyde compound into an ethanol-acetic acid mixed solution, and stirring and reacting at 65-75 ℃ for 12-24 h to react, wherein the aldehyde compound is one of 5-methyl salicylaldehyde, salicylaldehyde and 5-nitro salicylaldehydeAldehyde group-CHO in aldehyde compound and amino-NH in chitosan2The molar ratio is 2-6: 1, and after the reaction is finished, chitosan Schiff base powder is obtained through separation treatment;
b. putting chitosan Schiff base powder into a divalent copper ion solution, stirring for 3-9 h at 50-75 ℃ for divalent copper ion adsorption, and after adsorption, separating to obtain the chitosan Schiff base immobilized copper catalytic material Schiff-CS @ Cu.
8. The method for preparing allyl borate by using the modified chitosan copper material as claimed in claim 7, wherein the mixed solution of the ethanol and the acetic acid in the step a is prepared by mixing glacial acetic acid and absolute ethanol according to a volume ratio of 1: 7-8, and aldehyde-CHO in the aldehyde compound and amino-NH in the chitosan are obtained by mixing2The molar ratio was 4: 1.
9. The method for preparing allyl borate using modified chitosan copper material as claimed in claim 7, wherein Cu contained in the divalent copper ion solution in the step b2+With amino-NH in chitosan2The molar ratio is at least 1:1, and the concentration of copper ions in the divalent copper ion solution is 0.1-0.5 mol/L.
10. The method for preparing allyl borate using modified chitosan copper catalytic material as claimed in claim 7, wherein the separation process in steps a and b each comprises:
filtering, washing with anhydrous ethanol and distilled water alternately, and oven drying at 50 deg.C for 12 hr.
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| CN110590819A (en) * | 2019-08-28 | 2019-12-20 | 湖北工程学院 | Process for producing organoboron compound and process for producing beta-hydroxyorganoboron compound |
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| CN110590819A (en) * | 2019-08-28 | 2019-12-20 | 湖北工程学院 | Process for producing organoboron compound and process for producing beta-hydroxyorganoboron compound |
| CN112898326A (en) * | 2021-01-25 | 2021-06-04 | 湖北工程学院 | Preparation method and application of organic boron compound, and preparation method and application of beta-hydroxy compound |
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