CN114835738B - Method for preparing allyl borate by using biomass-based catalytic material - Google Patents
Method for preparing allyl borate by using biomass-based catalytic material Download PDFInfo
- Publication number
- CN114835738B CN114835738B CN202210455879.3A CN202210455879A CN114835738B CN 114835738 B CN114835738 B CN 114835738B CN 202210455879 A CN202210455879 A CN 202210455879A CN 114835738 B CN114835738 B CN 114835738B
- Authority
- CN
- China
- Prior art keywords
- catalytic material
- chitosan
- schiff
- copper
- biomass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 allyl borate Chemical compound 0.000 title claims abstract description 113
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 95
- 239000000463 material Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002028 Biomass Substances 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000000047 product Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 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 abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 4
- 229920001661 Chitosan Polymers 0.000 claims description 91
- 239000010949 copper Substances 0.000 claims description 60
- 239000002262 Schiff base Substances 0.000 claims description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 49
- 150000004753 Schiff bases Chemical class 0.000 claims description 49
- 229910052802 copper Inorganic materials 0.000 claims description 49
- 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 32
- 239000000843 powder Substances 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 16
- 238000004064 recycling Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical group OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 12
- CDXSJGDDABYYJV-UHFFFAOYSA-N acetic acid;ethanol Chemical compound CCO.CC(O)=O CDXSJGDDABYYJV-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 150000001299 aldehydes Chemical group 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 238000011282 treatment Methods 0.000 claims description 8
- ILEIUTCVWLYZOM-UHFFFAOYSA-N 2-hydroxy-5-methylbenzaldehyde Chemical group CC1=CC=C(O)C(C=O)=C1 ILEIUTCVWLYZOM-UHFFFAOYSA-N 0.000 claims description 6
- 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
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical group OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 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
- 238000001704 evaporation Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052796 boron Inorganic materials 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000007259 addition reaction Methods 0.000 abstract description 4
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- 238000007792 addition Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 125000000879 imine group Chemical group 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 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
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- MXOAEAUPQDYUQM-UHFFFAOYSA-N chlorphenesin Chemical group OCC(O)COC1=CC=C(Cl)C=C1 MXOAEAUPQDYUQM-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 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
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- GPKUICFDWYEPTK-UHFFFAOYSA-N methoxycyclohexatriene Chemical group COC1=CC=C=C[CH]1 GPKUICFDWYEPTK-UHFFFAOYSA-N 0.000 description 1
- XBCRXHRIVDBBQT-UHFFFAOYSA-N methyl 2-[acetyloxy-(4-methoxyphenyl)methyl]prop-2-enoate Chemical group COC(=O)C(=C)C(OC(C)=O)C1=CC=C(OC)C=C1 XBCRXHRIVDBBQT-UHFFFAOYSA-N 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
- 229910052763 palladium Inorganic materials 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
- 238000012805 post-processing Methods 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- 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
-
- 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
Landscapes
- 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)
Abstract
The application discloses a method for preparing allyl borate by using a biomass-based catalytic material, which comprises the following steps: 1) Adding MBH ester compound I, bisboronic acid pinacol ester and biomass-based catalytic material Schiff-CS@Cu into a pure water solvent, and mixing and stirring at room temperature for reaction for 12-24 hours; 2) And after the reaction is finished, filtering, separating and purifying the obtained filtrate to obtain allyl borate II, and washing and drying the precipitate to obtain the recovered catalytic material Schiff-CS@Cu. The catalytic material Schiff-CS@Cu has high catalytic activity, can be applied to catalyzing boron addition reactions of various MBH esters, takes pure water as a solvent, and is simple, convenient and easy to operate; has the advantages of small catalyst consumption, mild reaction condition, high product yield, etc. The yield of the obtained target product is more than 81%, and the yield of some specific allyl borates can exceed 90%.
Description
Technical Field
The application relates to the field of organic synthesis, in particular to a method for preparing allyl borate by using a biomass-based catalytic material.
Background
Allyl metal reagents, in which allyl borates are receiving attention because of excellent stability and low toxicity, easy availability and easy post-processing, have received attention in recent years because of their effective construction of C-C bonds in allylation reactions and cross-coupling reactions. MBH esters have a wide range of applications in organic synthesis due to the simultaneous alpha, beta-unsaturated carbonyl and allyl moietiesAnd (3) flooding. In 2004, the use of a divalent palladium salt Pd (OAc) was reported in the literature (J.org.chem.; 2004,69,5807.) 2 Catalyzing the boron addition of MBH esters gives allyl borates, which work uses 3 mole% Pd (OAc) 2 As a catalyst, toluene is added as a solvent, allyl borate is obtained by reaction at 50 ℃, and the reaction is performed with high efficiency of conversion of MBH ester to allyl borate, but noble metal is used as the catalyst in the reaction process, the catalyst dosage is large, and meanwhile, toluene as an organic solvent is used, so that the method is not friendly to the environment. In the same year, literature (org.lett., 2004,6,481.) reports the use of a monovalent copper salt, cuCl, to catalyze the boronation of MBH esters to give allylboronates, using CuCl as catalyst, liCl and KOAc as base additions, DMF (N, N-dimethylformamide) as solvent. Although the noble metal is avoided in the reaction, strong alkali and DMF as an organic solvent are added in the reaction process, so that the environment is polluted, and meanwhile, the monovalent copper salt of the catalyst is unstable and the operation is complex. Although the method realizes the conversion from MBH ester to allyl borate, the method has the problems of high cost, complicated operation, limited reaction conditions, environmental pollution, incapability of recycling the catalyst and the like, and the application of the method in practical production is greatly limited. Therefore, development of a new environment-friendly method which is low in cost, simple, convenient and easy to operate, mild in condition and capable of directly converting MBH ester into allyl borate in high yield is urgent.
Chitosan is obtained by deacetylation of chitin, the chitin is the second most abundant biopolymer in nature, the source is wide, the cost is low, and meanwhile, the chitosan is the only alkaline polysaccharide in nature, has no pollution to the environment, has the characteristics of good antibacterial property, biocompatibility, degradability and the like, but has the defects of poor mechanical strength, easiness in swelling and the like. The chitosan Schiff base material obtained by modifying chitosan with aldehyde compound not only can keep the characteristics of good antibacterial property, biocompatibility, degradability and the like of chitosan, but also can improve the physicochemical property of chitosan and the stability of chitosan. The chitosan Schiff base material structure contains a large number of imine groups and hydroxyl groups, is easy to coordinate with transition metal, and is widely applied in the field of catalysis. The construction of C-C bonds and C-N bonds is reported to be realized by using a chitosan Schiff base transition metal catalytic material obtained by modifying chitosan with aldehyde compounds to adsorb transition metals, but the construction of C-B bonds of the material is reported to be less so far.
Disclosure of Invention
The application aims to solve the defects of the background technology, provides a method for preparing allyl borate by using a biomass-based catalytic material, and aims to solve the problems that a catalyst in the prior art is expensive in metal, cannot be recycled, has high cost, is difficult to industrialize and the like to a certain extent.
The technical scheme of the application is as follows: a method for preparing allyl borate by using biomass-based catalytic material, which is characterized by comprising the following steps:
1) Adding MBH ester compound I, bisboronic acid pinacol ester and chitosan Schiff base supported copper catalytic material Schiff-CS@Cu into a pure water solvent, mixing and stirring at room temperature for reaction for 12-24 h, wherein the mass ratio of the MBH ester compound I is as follows: di-boric acid pinacol ester: the copper content=1 (1.2-2) (0.005-0.03) in the chitosan Schiff base immobilized copper catalytic material Schiff-CS@Cu, and the chemical reaction equation is as follows:
wherein R is 1 Phenyl, p-methylphenyl, p-methoxyphenyl, m-methoxyphenyl, o-chlorophenyl and p-chlorophenyl;
2) After the reaction is finished, filtering, separating and purifying the obtained filtrate to obtain allyl borate II, washing and drying the precipitate to obtain a recovered chitosan Schiff base copper catalytic material Schiff-CS@Cu, and carrying out the next recycling. In MBH ester compound I OAc is acetoxy, i.e. CH 3 COO-groups.
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, in step 1) MBH ester compound I: di-boric acid pinacol ester: the mass ratio of copper in the chitosan Schiff base immobilized copper catalytic material Schiff-CS@Cu is 1:2:0.01.
Preferably, the ratio of the dosage of the Schiff-CS@Cu supported copper and the dosage of pure water of the chitosan Schiff base supported copper catalytic material in the step 1) is 0.001-0.006mmol/2 ml.
Preferably, in step 1), the reaction is stirred at room temperature for 12 hours.
Preferably, the filtrate obtained in the step 2) is separated and purified to obtain allyl borate II, which specifically comprises the following steps: extracting the filtrate with ethyl acetate to obtain organic phase containing the product, and passing through anhydrous Na 2 SO 4 Drying, filtering, rotary evaporating to remove redundant organic solvent, and purifying the obtained residual organic phase by using ethyl acetate and petroleum ether mixed solvent column chromatography to obtain allyl borate II.
Preferably, the chitosan Schiff base immobilized copper catalytic material Schiff-CS@Cu in the step 1) is prepared by a method comprising the following steps of:
a. adding chitosan and aldehyde compound into ethanol acetic acid mixed solution, stirring at 65-75 ℃ for reacting for 12-24 hours, wherein the aldehyde compound is one of 5-methyl salicylaldehyde, salicylaldehyde and 5-nitro salicylaldehyde, and aldehyde group-CHO in the aldehyde compound and amino-NH in the chitosan 2 The molar ratio is 2-6:1, and after the reaction is finished, the chitosan Schiff base powder is obtained through separation treatment;
b. placing chitosan Schiff base powder into a cupric ion solution, stirring for 3-9 hours at 50-75 ℃ to adsorb cupric ions, and separating to obtain the chitosan Schiff base immobilized copper catalytic material Schiff-CS@Cu after adsorption is finished.
Further, the ethanol acetic acid mixed solution in the step a is obtained by mixing glacial acetic acid and absolute ethyl alcohol according to the volume ratio of 1:6-8, wherein aldehyde group-CHO in aldehyde compounds and amino-NH in chitosan 2 The molar ratio was 4:1. The acetic acid adopts the commercial glacial acetic acid, namely the mixed solution of anhydrous acetic acid and ethanol acetic acid as the solvent.
Further, cu contained in the cupric ion solution in the step b 2+ With amino-NH in chitosan 2 The molar ratio of copper in the cupric ion solution is at least 1:1The ion concentration is 0.1-0.5 mol/L. In the application, the cupric ion source is cupric sulfate pentahydrate, the cupric ion solution is cupric sulfate solution, and the chitosan Schiff base material loads the cupric ion solution through self adsorption.
Further, the separation processes in steps a and b each include: filtering, repeatedly and alternately washing with absolute ethyl alcohol and distilled water, and drying in an oven at 50 ℃ for 12 hours.
The application prepares allyl borate by chitosan Schiff base powder immobilized copper catalytic material. The chitosan Schiff base material contains a large amount of imine groups and unreacted complete amino groups in the material, so that an alkaline environment is provided for the whole reaction system, and no alkali is required to be added; in addition, the special space structure and biocompatibility of the chitosan Schiff base powder immobilized copper catalytic material are higher in catalytic activity and stronger in complexation; can be recycled, accords with the concept of green chemistry, and has wide industrial application prospect.
The beneficial effects of the application are as follows:
1. the chitosan Schiff base has good immobilization effect on metal copper, good biocompatibility, wide sources, low cost and environment friendliness. After the catalytic reaction is completed, the chitosan Schiff base supported copper catalytic material can be separated from other components in a reaction system by a solid-liquid phase separation method, can be reused after simple regeneration, reduces the production cost and is environment-friendly. Higher conversion can be achieved by using lower cost catalytic materials and lower amounts of catalytic materials.
2. In the process of preparing allyl borate by catalysis, alkali is not required to be added, the reaction is carried out at room temperature, the reaction condition is mild, and the operation is simple and easy; the higher conversion rate of the reactants can be realized only by using a catalyst with lower cost and lower catalyst dosage; the substrate has wide applicability, and can realize boron addition of MBH esters of different types to prepare corresponding allyl borate.
3. Chitosan Schiff base material pair Cu 2+ The adsorption of (2) is mainly based on imine group coordination, and the main reaction comprises:
schiff reaction of R' -NH 2 +RCHO→R′-N＝CHR (1)
After the biomass-based material chitosan is modified by the aldehyde compound, the coordination capacity of the chitosan is changed, and the catalytic activity of the catalyst is improved. Aldehyde group (rhc=o) of aldehyde compound and amino group (R' -NH) on chitosan 2 ) The Schiff base reaction is carried out to generate imine containing carbon-nitrogen double bond (R 2 C=nr' -) since the chitosan surface is rich in hydroxyl groups, the N atom in the c=n double bond formed by Schiff base reaction and the O atom in the adjacent OH are easy to react with Cu 2+ Multidentate coordination occurs, a stable conjugate plane is formed, and the complexing effect on copper ions is stronger.
4. When the aldehyde compound is used for modifying the chitosan, acetalation reaction can be carried out between aldehyde groups of the aldehyde compound and hydroxyl groups of the chitosan, and-C=O of the aldehyde compound is relative to-NH of chitosan unit bodies 2 With a large excess, sufficient imide groups are formed for forming stable complexes with copper ions. However, when the amount of the catalyst is too large, the O atom in the OH adjacent to the N atom in the C=N double bond is reduced by the acetal reaction, and the complexing effect on copper ions is reduced, so that when Schiff-CS@Cu, namely chitosan Schiff base powder is prepared, C=O in aldehyde and-NH of chitosan 2 A molar ratio of 4:1 is preferred.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the target product of example 4;
FIG. 2 is a nuclear magnetic resonance spectrum of the target product in example 4.
Detailed Description
The application is illustrated in further detail by the following specific examples. The drugs used in the examples are commercially available products unless otherwise specified, and the methods used are conventional in the art.
Example 1
The embodiment provides a method for preparing a Schiff-CS@Cu catalytic material L1 by modifying chitosan with 5-methyl salicylaldehyde, which comprises the following specific preparation processes:
a. preparation of chitosan Schiff base powder: chitosan powder (1.0 g) and 5-methyl salicylaldehyde (3.4 g) were added to a 85mL ethanol-acetic acid mixed solution (ethanol-acetic acid mixed solution was obtained by mixing 75mL absolute ethanol and 10mL glacial acetic acid), and the mixture was stirred at 65℃for reaction for 12 hours. Filtering to recover precipitate, repeatedly and alternately washing the precipitate with absolute ethyl alcohol and distilled water to remove unreacted 5-methyl salicylaldehyde, and drying in a baking oven at 50 ℃ for 12 hours to obtain chitosan Schiff base powder. The molecular formula of the chitosan is (C 6 H 11 NO 4 ) N,1.0g chitosan containing about 6.2mmol-NH 2 The amount of aldehyde used in this example is based on the aldehyde groups-CHO contained and the amino-NH group in chitosan 2 The molar ratio was determined to be 4:1. 5-methyl salicylaldehyde and-NH in chitosan 2 The Schiff reaction occurs and chitosan-NH is consumed 2 Generating imine group, changing coordination ability to metal and improving catalytic performance.
b. The chitosan Schiff base powder obtained in step a was added to 30mL of a copper sulfate solution (prepared from 1.6g of copper sulfate pentahydrate containing 6.4mmol of Cu) 2+ ) Stirring at 50deg.C for 6 hr, and filtering to separate Cu 2+ Repeatedly and alternately washing with absolute ethyl alcohol and distilled water to remove free copper ions and sulfate ions, and finally drying in an oven at 50 ℃ for 12 hours to obtain the Schiff-CS@Cu catalytic material denoted as 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 preparing a Schiff-CS@Cu catalytic material L2 by modifying chitosan with salicylaldehyde, which comprises the following specific preparation processes:
a. preparation of chitosan Schiff base powder: chitosan powder (1.0 g) and salicylaldehyde (3.0 g) were added to 85mL of an ethanol-acetic acid mixed solution (the ethanol-acetic acid mixed solution was obtained by mixing 75mL of absolute ethanol and 10mL of glacial acetic acid), and the mixture was stirred at 75℃for 18 hours. Filtering to recover precipitate, repeatedly and alternately washing the precipitate with absolute ethyl alcohol and distilled water to remove unreacted salicylaldehyde, and drying in a baking oven at 50 ℃ for 12 hours to obtain chitosan Schiff base powder. The molecular formula of the chitosan is (C 6 H 11 NO 4 )N，1.0The g chitosan contains about 6.2mmol-NH 2 The amount of aldehyde used in this example is based on the aldehyde groups-CHO contained and the amino-NH group in chitosan 2 The molar ratio was determined to be 4:1.
b. The chitosan Schiff base powder obtained in step a was added to 30mL of a copper sulfate solution (prepared from 1.6g of copper sulfate pentahydrate containing 6.4mmol of Cu) 2+ ) Stirring at 50deg.C for 6 hr, and filtering to separate Cu 2+ Repeatedly and alternately washing with absolute ethyl alcohol and distilled water to remove free copper ions and sulfate ions, and finally drying in an oven at 50 ℃ for 12 hours to obtain the Schiff-CS@Cu catalytic material denoted as L2.
The relative content of copper as active ingredient in L2 was found to be 0.877mmol/g by ICP.
Example 3
The embodiment provides a method for preparing a Schiff-CS@Cu catalytic material L3 by modifying chitosan with 5-nitro salicylaldehyde, which comprises the following specific preparation processes:
a. preparation of chitosan Schiff base powder: chitosan powder (1.0 g) and 5-nitrosalicylaldehyde (4.1 g) were added to a 85mL ethanol-acetic acid mixed solution (ethanol-acetic acid mixed solution was obtained by mixing 75mL absolute ethanol and 10mL glacial acetic acid), and reacted at 75℃with stirring for 24 hours. Filtering to recover precipitate, repeatedly and alternately washing the precipitate with absolute ethyl alcohol and distilled water to remove unreacted 5-nitro salicylaldehyde, and drying in a baking oven at 50 ℃ for 12 hours to obtain chitosan Schiff base powder. The molecular formula of the chitosan is (C 6 H 11 NO 4 ) N,1.0g chitosan containing about 6.2mmol-NH 2 The amount of aldehyde used in this example is based on the aldehyde groups-CHO contained and the amino-NH group in chitosan 2 The molar ratio was determined to be 4:1.
b. The chitosan Schiff base powder obtained in step a was added to 30mL of a copper sulfate solution (prepared from 1.6g of copper sulfate pentahydrate containing 6.4mmol of Cu) 2+ ) Stirring at 50deg.C for 6 hr, and filtering to separate Cu 2+ Repeatedly and alternately washing with absolute ethyl alcohol and distilled water to remove free copper ions and sulfate ions, and finally drying in an oven at 50 ℃ for 12 hours to obtain the Schiff-CS@Cu catalytic material denoted as L3.
The relative content of copper as an active ingredient in L3 was found to be 0.528mmol/g by ICP.
Comparative example
The embodiment provides a method for preparing a chitosan immobilized copper CS@Cu catalytic material L4, which comprises the following specific preparation processes:
chitosan powder (1.0 g) was added to 30mL of a copper sulfate solution (prepared from 1.6g of copper sulfate pentahydrate containing 6.4mmol of Cu) 2+ ) Stirring at 50deg.C for 6 hr, and filtering to separate Cu 2+ Repeatedly and alternately washing with absolute ethyl alcohol and distilled water to remove free copper ions and sulfate ions, and finally drying in an oven at 50 ℃ for 12 hours to obtain CS@Cu catalytic material denoted as L4.
The relative content of copper as an active ingredient in L4 was 1.75mmol/g as determined 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) MBH ester compound I, pinacol ester of bisboric acid and Schiff-CS@Cu catalytic material L3 (prepared in example 3) were added to 2ml of pure water, wherein 0.20mmol of MBH ester compound I, 0.40mmol of pinacol ester of bisboric acid and 0.002mmol of catalytic material L3 containing copper were mixed and stirred at room temperature for reaction for 12 hours, the MBH ester compound I of this example was methyl 2- (acetoxy (phenyl) methacrylate, wherein R 1 Is phenyl, and has the following reaction formula;
2) After the reaction is finished, filtering, repeatedly and alternately washing and drying a precipitate by using water and ethanol, recycling a chitosan Schiff base immobilized copper catalytic material Schiff-CS@Cu, extracting filtrate by using ethyl acetate (3X 10 mL) to obtain an organic phase containing a product, and carrying out anhydrous Na 2 SO 4 Drying, filtering and rotary steaming to remove redundant organic solvent. The remaining organic phase obtained was purified by column chromatography with ethyl acetate/petroleum ether mixed solvent=1:20 to give allyl borate II (R 1 Is phenyl). The yield of the product was 91% (55.0 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows, and the maps are shown in fig. 1 and 2.
1 H 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).
13 C NMR(100MHz,Chloroform-d)；δ＝169.2,137.7,136.3,130.2,129.5,128.4,128.1,83.6,52.2,24.8.
Example 4 shows that under the catalytic condition of the Schiff-CS@Cu catalytic material L3 provided in the example, the conversion rate of the 2- (acetoxy (phenyl) methyl acrylate is very high, and the yield of the boron addition product reaches 91%.
The catalytic material L1 prepared in example 1 was applied to the boron addition reaction of methyl 2- (acetoxy (phenyl) meth) acrylate with pinacol biborate in the above reaction procedure, with a yield of 57%.
The catalytic material L2 prepared in example 2 was applied to the boron addition reaction of methyl 2- (acetoxy (phenyl) meth) acrylate with pinacol biborate in the above reaction procedure with a yield of 72%.
The catalytic material L4 prepared in the comparative example was applied to the boron addition reaction of methyl 2- (acetoxy (phenyl) methyl) acrylate and pinacol diboronate in 61% yield in the above reaction steps.
Compared with the catalytic material L4 of the control group, the catalytic activity of the catalytic material L3 is improved, and the stronger the electron withdrawing capability of the substituent group at the 5 # position of the benzene ring of the salicylaldehyde compound is, the better the catalytic effect is. The salicylaldehyde compound has the aldehyde group positioned at the No. 2 position of the benzene ring and is a meta-position group of a substituent at the No. 5 position, the more obvious the group with stronger electron withdrawing capability activates the meta-position substituent, the more easily the reaction occurs, and the more imine groups are obtained by the reaction, 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 ester compound I, pinacol diboronate and Schiff-CS@Cu catalytic material L3 (prepared in example 3) were added to 2ml of pure water, wherein MBH0.20mmol of ester compound I, 0.40mmol of bisboronic acid pinacol ester and 0.002mmol of copper-containing catalytic material L3 are mixed and stirred at room temperature for reaction for 12h, the MBH ester compound I of the embodiment is 2- (acetoxy (p-tolyl) methyl) acrylate, wherein R 1 Is p-tolyl, and has the following reaction formula;
2) After the reaction is finished, filtering, repeatedly and alternately washing and drying a precipitate by using water and ethanol, recycling a chitosan Schiff base copper catalytic material, extracting filtrate by using ethyl acetate (3X 10 mL) to obtain an organic phase containing a product, and performing anhydrous Na treatment 2 SO 4 Drying, filtering and rotary steaming to remove redundant organic solvent. The remaining organic phase obtained was purified by column chromatography with ethyl acetate/petroleum ether mixed solvent=1:20 to give allyl borate II (R 1 P-tolyl). The product yield was 86% (54.4 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C NMR(100MHz,Chloroform-d)；δ＝169.5,138.3,137.9,133.5,129.6,129.4,129.2,83.6,52.2,24.9,21.5.
example 5 shows that under the catalytic condition of the Schiff-CS@Cu catalytic material L3 provided by the example of the application, the conversion rate of the 2- (acetoxy (p-tolyl) methyl acrylate is very high, and the yield of the boron addition product reaches 86%.
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) MBH ester compound I, pinacol ester of biboronate and Schiff-CS@Cu catalytic material L3 (prepared in example 3) were added to 2ml of pure water, wherein MBH ester compound I0.20 mmol, pinacol of biboronate0.40mmol of that alcohol ester and 0.002mmol of catalytic material L3 containing copper are mixed and stirred at room temperature for reaction for 12h, the MBH ester compound I of this example is 2- (acetoxy (p-methoxyphenyl) methyl) acrylic acid methyl ester, wherein R 1 Is p-methoxyphenyl and has the following reaction formula;
2) After the reaction is finished, filtering, repeatedly and alternately washing and drying a precipitate by using water and ethanol, recycling a chitosan Schiff base copper catalytic material for recycling, extracting filtrate by using ethyl acetate (3X 10 mL) to obtain an organic phase containing a product, and performing anhydrous Na treatment 2 SO 4 Drying, filtering again, and steaming to remove excessive organic solvent. The remaining organic phase obtained was purified by column chromatography with ethyl acetate/petroleum ether mixed solvent=1:20 to give allyl borate II (R 1 P-methoxyphenyl). The product yield was 81% (53.8 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product allyl borate II are shown as follows:
1 H 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).
13 C NMR(100MHz,Chloroform-d)；δ＝169.5,159.5,137.5,131.2,128.8,128.2,113.9,83.5,55.4,52.1,24.8.
example 6 shows that under the catalytic condition of the Schiff-CS@Cu catalytic material L3 provided by the example of the application, the conversion rate of the 2- (acetoxy (p-methoxyphenyl) methyl acrylate is very high, and the yield of the boron addition product reaches 81%.
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 ester compound I, pinacol diboronate and Schiff-CS@Cu catalytic material L3 (prepared in example 3) were added to 2ml of pure water, wherein MBH ester compound I0.20 mmol, unionThe reaction of pinacol borate 0.40mmol, catalytic material L3 containing copper 0.002mmol was carried out at room temperature with stirring for 12h, with the MBH ester compound I of this example being methyl 2- (acetoxy (m-methoxyphenyl) methacrylate, wherein R 1 Is m-methoxyphenyl and has the following reaction formula;
2) After the reaction is finished, filtering, repeatedly and alternately washing and drying a precipitate by using water and ethanol, recycling a chitosan Schiff base copper catalytic material for recycling, extracting filtrate by using ethyl acetate (3X 10 mL) to obtain an organic phase containing a product, and performing anhydrous Na treatment 2 SO 4 Drying, filtering and rotary steaming to remove redundant organic solvent. The remaining organic phase obtained was purified by column chromatography with ethyl acetate/petroleum ether mixed solvent=1:20 to give allyl borate II (R 1 Is m-methoxyphenyl). The product yield was 82% (54.5 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product allyl borate II are shown as follows:
1 H NMR(400MHz,Chloroform-d)；δ＝7.65(s,1H),7.29–6.83(m,4H),3.81(s,3H),3.80(s,3H),2.14(s,2H),1.23(s,12H).
13 C NMR(100MHz,Chloroform-d)；δ＝169.2,159.5,137.7,137.6,130.5,129.4,122.0,114.5,114.2,83.6,55.4,52.2,24.8.
example 7 shows that under the catalytic condition of the Schiff-CS@Cu catalytic material L3 provided by the example of the application, the conversion rate of the 2- (acetoxy (m-methoxyphenyl) methyl acrylate is very high, and the yield of the boron addition product reaches 82%.
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) MBH ester compound I, pinacol diboronate and Schiff-CS@Cu catalytic material L3 (prepared in example 3) were added to 2ml of pure water, wherein MBH ester compound I0.20 mmol, diboronAcid pinacol ester 0.40mmol, catalytic material L3 copper 0.002mmol, mixing and stirring at room temperature for reaction for 12h, the MBH ester compound I of this example is 2- (acetoxy (o-chlorophenyl) methyl) acrylate, wherein R 1 Is o-chlorophenyl, and has the following reaction formula;
2) After the reaction is finished, filtering, repeatedly and alternately washing and drying a precipitate by using water and ethanol, recycling a chitosan Schiff base copper catalytic material for recycling, extracting filtrate by using ethyl acetate (3X 10 mL) to obtain an organic phase containing a product, and performing anhydrous Na treatment 2 SO 4 Drying, filtering and rotary steaming to remove redundant organic solvent. The remaining organic phase obtained was purified by column chromatography with ethyl acetate/petroleum ether mixed solvent=1:20 to give allyl borate II (R 1 O-chlorophenyl). The product yield was 82% (55.2 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product allyl borate II are shown as follows:
1 H NMR(400MHz,Chloroform-d)；δ＝7.72(s,1H),7.42–7.38(m,2H),7.25–7.23(m,2H),3.81(s,3H),2.00(s,2H),1.24(s,12H).
13 C NMR(100MHz,Chloroform-d)；δ＝168.7,134.8,134.2,132.1,130.6,129.6,126.5,83.6,52.2,24.8.
example 8 shows that under the catalytic condition of the Schiff-CS@Cu catalytic material L3 provided by the example of the application, the conversion rate of the 2- (acetoxy (o-chlorophenyl) methyl acrylate is very high, and the yield of the boron addition product 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) MBH ester compound I, pinacol ester of bisboric acid and Schiff-CS@Cu catalytic material L3 (prepared in example 3) were added to 2ml of pure water, wherein MBH ester compound I0.20 mmol, pinacol ester of bisboric acid 0.40mmol, catalytic materialL3 copper 0.002mmol, mixing and stirring at room temperature for 12h, the MBH ester compound I of this example is methyl 2- (acetoxy (p-chlorophenyl) methyl) acrylate, wherein R 1 Is p-chlorophenyl, and has the following reaction formula;
2) After the reaction is finished, filtering, repeatedly and alternately washing and drying a precipitate by using water and ethanol, recycling a chitosan Schiff base copper catalytic material for recycling, extracting filtrate by using ethyl acetate (3X 10 mL) to obtain an organic phase containing a product, and performing anhydrous Na treatment 2 SO 4 Drying, filtering and rotary steaming to remove redundant organic solvent. The remaining organic phase obtained was purified by column chromatography with ethyl acetate/petroleum ether mixed solvent=1:20 to give allyl borate II (R 1 P-chlorophenyl). The product yield was 88% (59.2 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown below.
1 H 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).
13 C NMR(100MHz,Chloroform-d)；δ＝169.1,136.5,134.8,134.1,131.0,130.8,128.8,83.8,52.3,24.9.
Example 9 shows that under the catalytic condition of the Schiff-CS@Cu catalytic material L3 provided by the example of the application, the conversion rate of the 2- (acetoxy (p-chlorophenyl) methyl acrylate is very high, and the yield of the boron addition product reaches 88%.
Claims (9)
1. A method for preparing allyl borate by using biomass-based catalytic material, which is characterized by comprising the following steps:
1) Adding MBH ester compound I, bisboronic acid pinacol ester and chitosan Schiff base immobilized copper catalytic material Schiff-CS@Cu into pure water, mixing and stirring at room temperature for reacting for 12-24 h, wherein the mass ratio of the MBH ester compound I is as follows: di-boric acid pinacol ester: copper content=1 (1.2-2): (0.005-0.03) in the catalytic material Schiff-CS@Cu, and the chemical reaction equation is as follows:
wherein R is 1 Phenyl, p-methylphenyl, p-methoxyphenyl, m-methoxyphenyl, o-chlorophenyl and p-chlorophenyl;
the chitosan Schiff base immobilized copper catalytic material Schiff-CS@Cu is prepared by a method comprising the following steps of:
a. adding chitosan and aldehyde compound into ethanol acetic acid mixed solution, stirring at 65-75 ℃ for reacting for 12-24 hours, wherein the aldehyde compound is one of 5-methyl salicylaldehyde, salicylaldehyde and 5-nitro salicylaldehyde, and aldehyde group-CHO in the aldehyde compound and amino-NH in the chitosan 2 The molar ratio is 2-6:1, and after the reaction is finished, the chitosan Schiff base powder is obtained through separation treatment;
b. placing chitosan Schiff base powder into a cupric ion solution, stirring for 3-9 hours at 50-75 ℃ to adsorb cupric ions, and separating to obtain a chitosan Schiff base immobilized copper catalytic material Schiff-CS@Cu after adsorption is finished;
2) After the reaction is finished, filtering, separating and purifying the obtained filtrate to obtain allyl borate II, washing and drying the precipitate to obtain a recovered chitosan Schiff base copper catalytic material Schiff-CS@Cu, and carrying out the next recycling.
2. The method for preparing allyl borate by using biomass-based catalytic material as claimed in claim 1, wherein the copper content in the chitosan Schiff-cs@cu of step 1) is 0.5-1.4 mmol/g.
3. The method for preparing allyl borates using biomass-based catalytic materials according to claim 1, characterized in that in step 1) MBH ester compound I: di-boric acid pinacol ester: the catalytic material Schiff-CS@Cu contains copper in a mass ratio of 1:2:0.01.
4. The method for preparing allyl borate by using biomass-based catalytic material as claimed in claim 1, wherein the ratio of copper to pure water in the chitosan Schiff-CS@Cu supported copper catalytic material Schiff-CS@Cu in step 1) is 0.001-0.006mmol:2 ml.
5. The method for preparing allyl borate using biomass based catalytic material as claimed in claim 1, wherein the reaction is performed for 12 hours at room temperature with mixing and stirring in step 1).
6. The method for preparing allyl borate by using biomass-based catalytic material according to claim 1, wherein the filtrate obtained in the step 2) is separated and purified to obtain allyl borate II, specifically comprising: extracting the filtrate with ethyl acetate to obtain organic phase containing the product, and passing through anhydrous Na 2 SO 4 Drying, filtering, rotary evaporating to remove redundant organic solvent, and purifying the obtained residual organic phase by using ethyl acetate and petroleum ether mixed solvent column chromatography to obtain allyl borate II.
7. The method for preparing allyl borate by using biomass-based catalytic material as claimed in claim 1, wherein the ethanol acetic acid mixed solution in the step a is obtained by mixing glacial acetic acid and absolute ethyl alcohol according to a volume ratio of 1:7-8, wherein aldehyde-CHO in aldehyde compounds and amino-NH in chitosan 2 The molar ratio was 4:1.
8. The method for preparing allyl borate using biomass based catalytic material as claimed in claim 1, wherein the cupric ion solution in step b contains Cu 2+ With amino-NH in chitosan 2 The molar ratio is at least 1:1, and the concentration of copper ions in the cupric ion solution is 0.1-0.5 mol/L.
9. The method for preparing allyl borate using biomass-based catalytic material as claimed in claim 1, wherein the separation treatments in steps a and b each include: filtering, repeatedly and alternately washing with absolute ethyl alcohol and distilled water, and drying in an oven at 50 ℃ for 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210455879.3A CN114835738B (en) | 2022-04-27 | 2022-04-27 | Method for preparing allyl borate by using biomass-based catalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210455879.3A CN114835738B (en) | 2022-04-27 | 2022-04-27 | Method for preparing allyl borate by using biomass-based catalytic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114835738A CN114835738A (en) | 2022-08-02 |
| CN114835738B true CN114835738B (en) | 2023-09-29 |
Family
ID=82568533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210455879.3A Active CN114835738B (en) | 2022-04-27 | 2022-04-27 | Method for preparing allyl borate by using biomass-based catalytic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114835738B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573370A (en) * | 2017-09-19 | 2018-01-12 | 湖北工程学院 | The method that supported copper ion chitosan microball catalysis prepares organoboron compound and β hydroxy compounds |
| CN113429432A (en) * | 2021-06-30 | 2021-09-24 | 湖北工程学院 | Application of chitosan/cellulose composite microsphere immobilized copper in preparation of diphenyl silane compound |
| CN113509961A (en) * | 2021-06-30 | 2021-10-19 | 湖北工程学院 | Application of chitosan/cellulose composite microsphere immobilized copper in preparation of allylsilane compound |
-
2022
- 2022-04-27 CN CN202210455879.3A patent/CN114835738B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573370A (en) * | 2017-09-19 | 2018-01-12 | 湖北工程学院 | The method that supported copper ion chitosan microball catalysis prepares organoboron compound and β hydroxy compounds |
| CN113429432A (en) * | 2021-06-30 | 2021-09-24 | 湖北工程学院 | Application of chitosan/cellulose composite microsphere immobilized copper in preparation of diphenyl silane compound |
| CN113509961A (en) * | 2021-06-30 | 2021-10-19 | 湖北工程学院 | Application of chitosan/cellulose composite microsphere immobilized copper in preparation of allylsilane compound |
Non-Patent Citations (1)
| Title |
|---|
| andchitosanEliene Leandro de Araújo等.Synthesis, characterization and biological activity of Cu(II), Ni(II) andZn(II) complexes of biopolymeric Schiff bases of salicylaldehydes andchitosan.International Journal of Biological Macromolecules.2016,第95卷168-176. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114835738A (en) | 2022-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113563370B (en) | Preparation method for preparing beta-boron-based ketone with alpha-position substituent by catalysis of chitosan loaded copper material | |
| CN112592361B (en) | Fluoroboropyrrole functionalized metal organic framework material and preparation method and application thereof | |
| CN113429432B (en) | Application of chitosan/cellulose composite microsphere immobilized copper in preparation of diphenyl silane compound | |
| CN108298499B (en) | Method for decomposing and releasing hydrogen by catalyzing formic acid with water-soluble metal complex | |
| CN113509961B (en) | Application of chitosan/cellulose composite microsphere immobilized copper in preparation of allylsilane compound | |
| CN113457736B (en) | Application of chitosan/cellulose composite microsphere immobilized copper in catalyzing silicon addition reaction of alpha, beta-unsaturated carbonyl compound | |
| CN112321628B (en) | Preparation method of beta-dimethylphenyl silicon substituted organic nitrile compound | |
| CN114478576A (en) | Synthetic method of spiroheterocyclic compound | |
| CN114835738B (en) | Method for preparing allyl borate by using biomass-based catalytic material | |
| CN102850153A (en) | Asymmetric reduction reaction method for catalyzing alpha, beta-unsaturated ketene and saturated ketene | |
| CN102304062B (en) | Method for preparing Salen Ni | |
| CN114456203B (en) | Method for preparing beta-boron-based ketone by catalysis of chitosan Schiff base copper functional material | |
| CN114656494A (en) | Method for preparing allyl borate by using modified chitosan copper material | |
| CN114605451A (en) | Method for preparing beta-boron amide based on chitosan functionalized copper material | |
| CN114602555A (en) | Preparation method and application of chitosan Schiff base immobilized copper material | |
| CN115634718B (en) | Preparation method and application of graphene oxide/chitosan/polyvinyl alcohol composite microsphere immobilized copper catalyst | |
| CN1226099C (en) | Chiral iridium catalyst and its preparation method and its application in industrial synthesis of chiral alcohol | |
| CN116969987A (en) | Method for preparing 1,2,3, 4-disilyl tetrahydroquinoline compound by utilizing chitosan Schiff base copper functional material | |
| CN115340563A (en) | Preparation method of allyl boron compound and zinc-catalyzed cyclopropene | |
| CN117567436A (en) | Novel fluorescent dialdehyde compound, preparation method, chitosan Schiff base copper functional material and application thereof | |
| CN116102586B (en) | Method for synthesizing diaryl silicon-based methane | |
| CN117186135A (en) | CS-SA-PNIPAAm@Cu 2+ Application of catalyst in synthesis of chiral organoboron compounds | |
| RU2258561C1 (en) | Palladium-containing hydrogenation catalyst preparation method | |
| CN111302880B (en) | Application of iron catalyst in reduction coupling reaction and preparation method of aromatic ring and heterocyclic derivative | |
| CN110605143B (en) | Application of organic iron salt as catalyst in synthesis of alkyl boron ester compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |