CN115463689A - Method for catalyzing Suzuki-Miyaura coupling reaction by cellulose aerogel supported catalyst - Google Patents
Method for catalyzing Suzuki-Miyaura coupling reaction by cellulose aerogel supported catalyst Download PDFInfo
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- CN115463689A CN115463689A CN202211114785.6A CN202211114785A CN115463689A CN 115463689 A CN115463689 A CN 115463689A CN 202211114785 A CN202211114785 A CN 202211114785A CN 115463689 A CN115463689 A CN 115463689A
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- cellulose aerogel
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- 239000004964 aerogel Substances 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 239000001913 cellulose Substances 0.000 title claims abstract description 44
- 229920002678 cellulose Polymers 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 title claims abstract description 42
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 35
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 16
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960000583 acetic acid Drugs 0.000 claims abstract description 8
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 238000007710 freezing Methods 0.000 claims abstract description 7
- 230000008014 freezing Effects 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 73
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000003755 preservative agent Substances 0.000 claims description 6
- 230000002335 preservative effect Effects 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 150000001502 aryl halides Chemical class 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 240000000560 Citrus x paradisi Species 0.000 claims 3
- 238000002360 preparation method Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 12
- 238000011160 research Methods 0.000 abstract description 3
- 244000276331 Citrus maxima Species 0.000 description 51
- 235000001759 Citrus maxima Nutrition 0.000 description 44
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 230000003197 catalytic effect Effects 0.000 description 23
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 6
- 125000006575 electron-withdrawing group Chemical group 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
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- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 230000000051 modifying effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000006880 cross-coupling reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- HQSCPPCMBMFJJN-UHFFFAOYSA-N 4-bromobenzonitrile Chemical compound BrC1=CC=C(C#N)C=C1 HQSCPPCMBMFJJN-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- 238000006464 oxidative addition reaction Methods 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 1
- AITNMTXHTIIIBB-UHFFFAOYSA-N 1-bromo-4-fluorobenzene Chemical compound FC1=CC=C(Br)C=C1 AITNMTXHTIIIBB-UHFFFAOYSA-N 0.000 description 1
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001499 aryl bromides Chemical class 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
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- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006478 transmetalation reaction Methods 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- GQHWSLKNULCZGI-UHFFFAOYSA-N trifluoromethoxybenzene Chemical compound FC(F)(F)OC1=CC=CC=C1 GQHWSLKNULCZGI-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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Abstract
The invention discloses a method for catalyzing Suzuki-Miyaura coupling reaction by using cellulose aerogel supported catalyst, which comprises the following steps: s1, preparing cellulose aerogel (GPA); s2, preparing modified cellulose aerogel (M-GPA): putting the cellulose aerogel obtained in the step S1 into a beaker containing a mixed solution of absolute ethyl alcohol, glacial acetic acid and methyltrimethoxysilane, and soaking for 8-10h at room temperature; and after soaking, washing the obtained product with distilled water to be neutral, replacing the obtained product with tert-butyl alcohol, standing at room temperature for 12 hours, freezing the obtained product in a refrigerator for 24 hours, taking out the obtained product, putting the obtained product in a freeze dryer, and freeze-drying the obtained product at 80 ℃ for 72 hours, and taking out the obtained product to obtain the modified cellulose aerogel. According to the method for catalyzing the Suzuki-Miya ura coupling reaction by using the cellulose aerogel supported catalyst, the yield of the Suzuki-Miya ura coupling reaction is ensured, the palladium acetate catalyst is recycled for multiple times, the test cost is greatly reduced, and the research and application of the supported palladium acetate are promoted.
Description
Technical Field
The invention relates to the technical field of catalyst immobilization, in particular to a method for catalyzing Suzuki-Miyaura coupling reaction by using a cellulose aerogel supported catalyst.
Background
At present, suzuki-Miyaura coupling reaction has the advantages of wide substrate application range, mild reaction conditions, stability to heat, air and water, no toxicity of byproducts, easiness in aftertreatment and the like, and is widely applied to laboratory synthesis and industrial synthesis of organic fine products and medicines.
The catalytic cycling process of the Suzuki-Miyaura coupling reaction generally comprises the elementary reactions of oxidative addition, metal transfer, reduction elimination and the like. The beginning of the catalytic cycle is the oxidative addition reaction of an organic electrophile with zero-valent palladium to form R 1 The divalent Pd-X intermediate is then subjected to a transmetallation reaction with an organic boride to form R 1 -Pd-R 2 Intermediate, finally reduced and eliminated to obtain coupled product R 1 -R 2 And simultaneously, the palladium with zero valence state is released to participate in the catalytic cycle again.
However, during the process of catalyzing Suzuki-Miyaura coupling reaction by palladium acetate, palladium black is easily formed, which not only affects the experiment, but also reduces the yield and increases the consumption of palladium acetate. And palladium acetate is expensive, and the large consumption of palladium acetate increases the experiment cost.
The current supported palladium acetate mostly uses silica gel, and the conversion rate of the supported palladium acetate catalyzing the Suzuki-Miyaura coupling reaction is far lower than that of homogeneous palladium acetate.
Disclosure of Invention
The invention aims to provide a method for catalyzing Suzuki-Miyaura coupling reaction by using a cellulose aerogel supported catalyst, and solves the problems of high consumption of palladium acetate, high experiment cost and low conversion rate of supported palladium acetate in the background technology.
In order to achieve the purpose, the invention provides a method for catalyzing Suzuki-Miyaura coupling reaction by using cellulose aerogel supported catalyst, which comprises the following steps:
s1, preparing cellulose aerogel (GPA);
s2, preparing modified cellulose aerogel (M-GPA): putting the cellulose aerogel obtained in the step S1 into a beaker containing a mixed solution of absolute ethyl alcohol, glacial acetic acid and methyltrimethoxysilane, and soaking for 8-10h at room temperature; after soaking, washing the mixture with distilled water to be neutral, replacing the neutral solution with tert-butyl alcohol, standing the mixture at room temperature for 12 hours, freezing the mixture in a refrigerator for 24 hours, taking the mixture out, putting the mixture into a freeze dryer, and freeze-drying the mixture at 80 ℃ for 72 hours, and taking the mixture out to obtain modified cellulose aerogel;
s3, fixing palladium acetate (preparing a catalyst Pd/M-GPA): dissolving 5-10 mg of palladium acetate in 5-15 mL of dichloromethane, placing the dichloromethane into a beaker, adding 35-45 mg of modified cellulose aerogel, sealing the beaker by using a preservative film, placing the beaker into a low-temperature constant-temperature stirring reaction bath, fixing the rotating speed, stirring for 16-24 h, and then placing the beaker at room temperature for drying for 24h to obtain the catalyst Pd/M-GPA.
Preferably, in step S1, the cellulose aerogel (GPA) is prepared by: cutting fresh pomelo peel into cuboid blocks with proper size, placing the cuboid blocks into a beaker, sealing the opening by using a preservative film, placing the beaker into a freeze dryer, freeze-drying the pomelo peel for 4 days at 80 ℃, and taking out the pomelo peel to obtain the cellulose aerogel.
Preferably, the step of the Suzuki-Miyaura coupling reaction is: sequentially adding aryl halide, phenylboronic acid, potassium carbonate and Pd/M-GPA into p-xylene, and stirring and reacting for 20-60 minutes at the temperature of 300R in the reflux atmosphere of the ambient atmosphere at 130-150 ℃; after the reaction was completed (detected by TLC), the catalyst Pd/M-GPA was removed; the organic phase was then evaporated under reduced pressure leaving the crude product which was further purified by silica gel column chromatography to give the desired cross-coupled product.
Preferably, the mass fractions of the absolute ethyl alcohol, the glacial acetic acid and the methyltrimethoxysilane in the mixed solution are respectively as follows: 97wt% of absolute ethyl alcohol, 1wt% of glacial acetic acid and 1wt% of methyltrimethoxysilane.
Preferably, in step S3, the amount of palladium acetate added is 0.01 to 0.015% of the molar amount of phenylboronic acid.
Preferably, in the step S3, the modified shaddock peel aerogel accounts for 0.3 to 0.7wt% of the total weight of the modified shaddock peel aerogel.
Preferably, in step S3, the low-temperature isothermal stirring reaction bath temperature is set to 20 to 25 ℃.
Therefore, the method for catalyzing the Suzuki-Miyaura coupling reaction by using the cellulose aerogel supported catalyst ensures the yield of the Suzuki-Miyaura coupling reaction, realizes the repeated cyclic utilization of the palladium acetate catalyst, greatly reduces the test cost, and promotes the research and application of the supported palladium acetate.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a scanning electron microscope image of the shaddock peel aerogel with different magnifications before and after modification in the method for catalyzing Suzuki-Miyaura coupling reaction by using the cellulose aerogel supported catalyst;
FIG. 2 is a scanning electron microscope image of different magnifications of Pd (OAc) 2 adsorbed by the shaddock peel aerogel before and after modification in the method for catalyzing Suzuki-Miyaura coupling reaction by using the cellulose aerogel supported catalyst;
FIG. 3 is an XRD (X-ray diffraction) spectrum of the shaddock peel cellulose aerogel before and after modification in the method for catalyzing Suzuki-Miyaura coupling reaction by using the cellulose aerogel supported catalyst;
FIG. 4 is an XRD (X-ray diffraction) spectrum of palladium acetate adsorbed by shaddock peel cellulose aerogel before and after modification of a method embodiment of catalyzing a Suzuki-Miyaura coupling reaction by using a cellulose aerogel supported catalyst;
FIG. 5 is a catalytic cycle test of the catalyst Pd/M-GPA-1 in the method for catalyzing Suzuki-Miyaura coupling reaction by using the cellulose aerogel supported catalyst.
Detailed Description
The technical solution of the present invention is further illustrated by the accompanying drawings and examples.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example one
A method for catalyzing Suzuki-Miyaura coupling reaction by using a cellulose aerogel supported catalyst comprises the following steps:
s1, preparing shaddock peel aerogel (GPA): cutting fresh pomelo peel into regular cuboid blocks of 2.5cm × 2.8cm × 1.8cm, placing the cuboid blocks into a 50mL plastic beaker, sealing the plastic beaker by using a preservative film, placing the plastic beaker into a freeze dryer, freeze-drying the plastic beaker at 80 ℃ for 4 days, and taking out the plastic beaker to obtain pomelo peel aerogel;
s2, preparing modified shaddock peel aerogel (M-GPA): placing the shaddock peel aerogel obtained in the step S1 into a beaker containing a mixed solution of 97mL of absolute ethyl alcohol, 1mL of glacial acetic acid and 1mL of methyltrimethoxysilane, and soaking for 9 hours at room temperature; after soaking, washing with distilled water to be neutral, then replacing with tert-butyl alcohol, standing at room temperature for 12h, freezing in a refrigerator for 24h, taking out, putting in a freeze dryer, freeze-drying at 80 ℃ for 72h, and taking out to obtain methyltrimethoxysilane modified shaddock peel aerogel (M-GPA-1);
s3, fixing palladium acetate (preparing a catalyst Pd/M-GPA): dissolving 5mg of palladium acetate in 5mL of dichloromethane, placing the dichloromethane in a 50mL beaker, adding 37mg of M-GPA, sealing the beaker by using a preservative film, placing the sealed beaker in a low-temperature constant-temperature stirring reaction bath, setting the temperature of the low-temperature constant-temperature stirring reaction bath to be 20 ℃, fixing the rotating speed, and stirring for 24 hours; then the solution is dried for 24 hours at room temperature to obtain the catalyst Pd/M-GPA-1.
In the step S3, the adding amount of palladium acetate is 0.01-0.015 percent of the molar weight of phenylboronic acid during the Suzuki-Miyaura coupling reaction, and the mass fraction of the modified shaddock peel aerogel is 0.3-0.7 percent.
Example two
Palladium acetate was loaded on unmodified shaddock peel aerogel to obtain Pd/GPA under the same experimental conditions as in example one.
EXAMPLE III
The method is the same as the experimental conditions of the first embodiment, sodium sulfide is used for modifying the shaddock peel aerogel, and the method comprises the following specific steps:
on the basis of the shaddock peel aerogel obtained in the step S1, adding a sodium sulfide solution with a concentration of 1.5mol/L according to the ratio of shaddock peel aerogel to the sodium sulfide solution =1:5, uniformly stirring with a glass rod, standing at room temperature for 12 hours, then washing with distilled water for multiple times until the solution is neutral, and detecting with a pH test paper.
And (2) after water washing to be neutral, replacing with tert-butyl alcohol, standing at room temperature for 12h, freezing in a refrigerator for 24h, taking out, putting in a freeze dryer, freeze-drying at 80 ℃ for 72h, and taking out to obtain the shaddock peel aerogel (M-GPA-2) modified by sodium sulfide.
Palladium acetate was then loaded on the sodium sulfide modified shaddock peel aerogel according to the procedure of example one S3 to obtain the catalyst Pd/M-GPA-2.
Example four
The method is the same as the experimental conditions of the first embodiment, potassium hydroxide is used for modifying the shaddock peel aerogel, and the method comprises the following specific steps:
on the basis of the shaddock peel aerogel obtained in the step S1, KOH is used as an active agent, the shaddock peel aerogel and a potassium hydroxide (25%) solution are mixed according to the mass ratio of 1:3, and after the shaddock peel aerogel and the potassium hydroxide (25%) solution are soaked for 12 hours at room temperature, the shaddock peel aerogel and the potassium hydroxide are washed to be neutral for many times by using distilled water and detected by using a pH test paper.
And (2) after water washing to be neutral, replacing with tert-butyl alcohol, standing at room temperature for 12h, putting into a refrigerator for freezing for 24h, taking out, putting into a freeze dryer, freeze-drying at 80 ℃ for 72h, and taking out to obtain the pomelo peel aerogel (M-GPA-3) modified by potassium hydroxide.
Palladium acetate was then loaded on a shaddock peel aerogel modified with potassium hydroxide according to the procedure in example one S3 to obtain the catalyst Pd/M-GPA-3.
EXAMPLE five
The method is the same as the experimental conditions of the first embodiment, and the shaddock peel aerogel is modified by using dipotassium hydrogen phosphate, and the method comprises the following specific steps:
based on the shaddock peel aerogel obtained in the step S1, K is added 2 HPO 4 The shaddock peel aerogel and dipotassium hydrogen phosphate (25%) solution are mixed according to the mass ratio of 1:3 to serve as an active agent, and after the shaddock peel aerogel and the dipotassium hydrogen phosphate (25%) solution are soaked for 12 hours at room temperature, the shaddock peel aerogel and the dipotassium hydrogen phosphate are washed to be neutral for multiple times by using distilled water, and the pH test paper is used for detecting the active agent.
Washing with water to neutrality, replacing with tert-butanol, standing at room temperature for 12h, freezing in refrigerator for 24h, taking out, freeze drying in freeze drier at 80 deg.C for 72h, and taking out to obtain pericarpium Citri Grandis aerogel (M-GPA-4) modified with dipotassium hydrogen phosphate.
Palladium acetate was then loaded on a shaddock peel aerogel modified with potassium hydroxide according to the procedure in example one S3 to obtain the catalyst Pd/M-GPA-4.
Experimental testing
Performing electron microscope scanning with different magnifications on powdery samples of the shaddock peel aerogel and the modified shaddock peel aerogel. As shown in fig. 1, a and b are electron micrographs of modified shaddock peel aerogel; c is an electron microscope picture of the shaddock peel aerogel modified by the methyltrimethoxysilane; d is a partial enlarged view of fig. c; e. f is an electron microscope picture of sodium sulfide modified shaddock peel aerogel; g is an electron microscope picture of potassium hydroxide modified shaddock peel aerogel; h is a partial enlarged view of fig. g; i is an electron microscope picture of the shaddock peel aerogel modified by dipotassium hydrogen phosphate; j is a partial enlarged view of fig. i.
The result shows that the modified shaddock peel aerogel has a cellular porous structure, a large number of fine pore channels, multiple rows of internal pore shapes, close arrangement among layered structures and a loose cellular structure rule. The modified shaddock peel aerogel surface shows a 3D interconnected porous structure, has a plurality of small holes uniformly distributed, and shows an irregular-shaped plant sheet tissue. Each porous structure loosely fills the open space. The modifying effect of the modifying agent in the embodiment on the pomelo peel aerogel is proved to be better.
And (II) respectively testing the catalysts Pd/GPA and Pd/M-GPA by using a scanning electron microscope. As shown in FIG. 2, a and b are SEM images of Pd/GPA; c. d is an SEM image of Pd/M-GPA-1; e. f is an SEM image of Pd/M-GPA-2; g. h is an SEM image of Pd/M-GPA-3; i. j is the SEM image of Pd/M-GPA-4.
Compared with a scanning electron microscope image of the fig. 1 which does not adsorb palladium acetate, the palladium acetate is loaded on the shaddock peel aerogel and the modified shaddock peel aerogel to generate catalysts Pd/GPA and Pd/M-GPA, the shapes of the catalysts Pd/GPA and Pd/M-GPA are almost not obviously changed from those of the catalysts GPA and M-GPA, and the catalysts are still in a three-dimensional reticular porous spatial structure and have plant sheet tissues with regular shapes. The original shape structure of the carrier GPA and the carrier M-GPA still keeps after loading palladium acetate to generate the catalyst.
And (III) respectively carrying out XRD (X-ray diffraction) spectrum inspection on the shaddock peel aerogel, the modified shaddock peel aerogel, the catalysts Pd/GPA and the Pd/M-GP A, as shown in figures 3 and 4.
As can be seen from the figure, the diffraction peaks of the carrier GPA and the catalyst Pd/M-GPA are consistent, and the condition that the crystal structures of the GPA and the M-GPA are not damaged after the palladium acetate and the GPA are coordinated with the M-GPA is shown. And a newly generated characteristic diffraction peak of Pd/GPA at 2 θ =38.78 ° is a (111) crystal plane of Pd (ii), and a newly generated characteristic diffraction peak of Pd/M-GPA at 2 θ =39.06 ° is a (111) crystal plane of Pd (ii). Therefore, the palladium acetate is further shown to be attached to the shaddock peel aerogel before and after modification, and catalysts Pd/GPA and Pd/M-GPA are generated.
And (IV) respectively putting two catalysts, namely Pd/GPA and Pd/M-GPA, into a Suzuki coupling reaction by taking bromobenzene (39mg, 0.25mmol) and phenylboronic acid (61mg, 0.5mmol) as reactants, and analyzing by Gas Chromatography (GC) to calculate the yield so as to obtain the catalyst for the optimal reaction.
The experimental steps of the Suzuki-Miyaura coupling reaction are as follows: sequentially adding aryl halide, phenylboronic acid, potassium carbonate and Pd/M-GPA into p-xylene, and stirring and reacting for 20-60 minutes at 130-150 ℃ in an ambient atmosphere reflux atmosphere; after the reaction was completed (detected by TLC), the catalyst Pd/M-GPA was removed; the organic phase was then evaporated under reduced pressure leaving the crude product which was further purified by silica gel column chromatography to give the desired cross-coupled product.
The Suzuki-Miyaura coupling reaction was as follows, using different catalysts in the process, with the results shown in table 1.
TABLE 1 selection of catalysts in Suzuki coupling reactions
As can be seen from Table 1, the effect of the Suzuki coupling reaction catalyzed by the catalyst Pd/M-GPA-1 is the best, and a cross-coupling product is provided with excellent yield (96%), which proves that the effect of the methyltrimethoxysilane modified shaddock peel aerogel supported catalyst in the first example is the best.
(V) Using Pd/M-GPA-1 prepared in example one as a catalyst, a Suzuki-Miyaura coupling reaction of bromobenzene and phenylboronic acid as a model reaction, which was subjected to extension of the reactant substrate and was K 2 CO 3 And p-xylene as a base and solvent the activity of the catalyst was examined.
The Suzuki-Miyaura coupling reaction was as follows, during which a catalytic activity test was carried out using Pd/M-GPA-1 as a catalyst, and the results are shown in Table 2.
TABLE 2 catalytic Activity test of Pd/M-GPA-1 in the Suzuki-Miyaura coupling reaction
| Entry a | R 1 | X | Yield(％) b |
| 1 | H | Br | 96％ |
| 2 | H | I | 97％ |
| 3 | F | Br | 94％ |
| 4 | Cl | Br | 94％ |
| 5 | NO 2 | Br | 91％ |
| 6 | OCF 3 | Br | 96％ |
| 7 | CN | Br | 76％ |
As can be seen from Table 2, the substituted functional group of the aryl halide has an effect on the rate of coupling reaction when the catalyst Pd/M-GPA-1 catalyzes the Suzuki-Miyaura coupling reaction, the order of ease of reaction is RI > RBr (Entry 1-2), and cross-coupling products are provided in excellent yields (96-97%). Then, the electronic effects of different substituents of the aryl bromide are researched, and when an electron-withdrawing group exists, such as fluorine, chlorine, nitro and trifluoromethoxy (Entry 3-6), a cross-coupling product is obtained with excellent yield (91-96%), which indicates that the coupling reaction is facilitated when the electron-withdrawing group is connected to the benzene ring of the bromobenzene substrate.
Wherein, the yield of the coupling product obtained by the Suzuki-Miyaura coupling reaction of the bromo-arene with the electron-withdrawing group (-CN) is lower than that of other electron-withdrawing groups because the positioning effect of the electron-withdrawing group in the 4-bromobenzonitrile is the meta-position of the benzene ring, -CH is arranged between the-CN and the benzene ring 2 Thus the directing group is actually-CH 2 CN, which has only electron-withdrawing induction effect but no electron-withdrawing conjugation effect, is an ortho-para positioning group for passivating benzene ring. The results show that the catalyst Pd/M-GPA-1 has high catalytic activity in catalyzing Suzuki-Miyaura coupling reaction.
(VI) catalytic cycle test of the catalyst Pd/M-GPA-1.
The reaction mixture was stirred at 140 ℃ and reacted at ambient atmospheric reflux for 20 minutes using bromobenzene (39mg, 0.25mmol), phenylboronic acid (61mg, 0.5mmol), potassium carbonate (138mg, 1.0 mmol), pd/M-GPA-1 (35mg, 1.0 mol%), and 4mL of p-xylene. After the reaction is finished, the catalyst Pd/M-GPA-1 is taken out, rinsed and extracted by ethyl acetate, and the recovered catalyst is dried for 24 hours at room temperature and then is directly used. The product was extracted with ethyl acetate, analyzed by Gas Chromatography (GC), and the yield was calculated. Under the same conditions, the catalyst was used four times in succession. And the bromobenzene can be replaced by other reactant substrates to carry out a catalytic cycle experiment.
The results of catalytic cycling experiments on different reactant substrates are shown in FIG. 5, where a is the catalytic cycle of bromobenzene, b is the catalytic cycle of iodobenzene, c is the catalytic cycle of 1-bromo-4-fluorobenzene, d is the catalytic cycle of 4-bromochlorobenzene, e is the catalytic cycle of 1-bromo-4- (trifluoromethoxybenzene), f is the catalytic cycle of 1-bromo-4-nitrobenzene, and g is the catalytic cycle of 4-bromobenzonitrile.
As can be seen from the figure, the catalytic activity of the catalyst Pd/M-GPA-1 is obviously reduced after being continuously recycled for 3 to 4 times in the catalytic process. The activity of the common palladium catalyst is reduced very quickly in the using process, and the common palladium catalyst needs to be activated again after being used for one time basically to participate in the reaction.
The reason for the reduction of the catalytic activity of the catalyst Pd/M-GPA-1 in the experiment is that: halogenated aromatic hydrocarbon of the Suzuki-Miyaura coupling reaction firstly interacts with a catalyst, the halogenated aromatic hydrocarbon can be adsorbed on active sites on the surfaces of nanoparticles, the active sites are mainly located at edge points and vertexes of the nanoparticles, and the adsorption performance of the sites is lowest. Secondly, aggregation and dissociation of the palladium nano catalyst also have certain influence on the catalytic activity of the catalyst, when the nano palladium particles are heated, the palladium atoms of the catalyst on the surface are separated from the particles and enter the solution to perform a catalytic action on free palladium atoms, and simultaneously the free palladium atoms in the solution are aggregated to the surface of the palladium particles again to form dynamic balance, so that the aggregation phenomenon of the nano palladium is promoted by the increase of the environmental temperature, large-particle nano palladium particles are generated, the catalytic activity is reduced, and even palladium black is generated to inactivate.
Therefore, the method for catalyzing the Suzuki-Miyaura coupling reaction by using the cellulose aerogel supported catalyst ensures the yield of the Suzuki-Miyaura coupling reaction, realizes the repeated cyclic utilization of the palladium acetate catalyst, greatly reduces the test cost, and promotes the research and application of the supported palladium acetate.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (8)
1. A method for catalyzing Suzuki-Miyaura coupling reaction by using cellulose aerogel supported catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing cellulose aerogel (GPA);
s2, preparing modified cellulose aerogel (M-GPA): putting the cellulose aerogel obtained in the step S1 into a beaker containing a mixed solution of absolute ethyl alcohol, glacial acetic acid and methyltrimethoxysilane, and soaking for 8-10h at room temperature; after soaking, washing the mixture with distilled water to be neutral, replacing the neutral solution with tert-butyl alcohol, standing the mixture at room temperature for 12 hours, freezing the mixture in a refrigerator for 24 hours, taking the mixture out, putting the mixture into a freeze dryer, and freeze-drying the mixture at 80 ℃ for 72 hours, and taking the mixture out to obtain modified cellulose aerogel;
s3, fixing palladium acetate (preparing a catalyst Pd/M-GPA): dissolving 5-10 mg of palladium acetate in 5-15 mL of dichloromethane, placing the dichloromethane in a beaker, adding 35-45 mg of modified cellulose aerogel, sealing the beaker by using a preservative film, placing the beaker in a low-temperature constant-temperature stirring reaction bath, fixing the rotating speed, stirring for 16-24 h, and then placing the beaker at room temperature for drying for 24h to obtain the catalyst Pd/M-GPA.
2. The method for catalyzing Suzuki-Miy aura coupling reaction by using the cellulose aerogel supported catalyst according to claim 1, wherein the method comprises the following steps: in step S1, the preparation process of the cellulose aerogel (GPA) is: cutting fresh pomelo peel into cuboid blocks with proper size, placing the cuboid blocks into a beaker, sealing the opening by using a preservative film, placing the beaker into a freeze dryer, freeze-drying the pomelo peel for 4 days at 80 ℃, and taking out the pomelo peel to obtain the cellulose aerogel.
3. The method for catalyzing Suzuki-Miy aura coupling reaction by using the cellulose aerogel supported catalyst according to claim 1, wherein the method comprises the following steps: the Suzuki-Miyaura coupling reaction comprises the following steps: sequentially adding aryl halide, phenylboronic acid, potassium carbonate and Pd/M-GPA into p-xylene, and stirring and reacting for 20-60 minutes at 130-150 ℃ in an ambient atmosphere reflux atmosphere; after the reaction was completed (detected by TLC), the catalyst Pd/M-GPA was removed; the organic phase was then evaporated under reduced pressure leaving the crude product which was further purified by silica gel column chromatography to give the desired cross-coupled product.
4. The method for catalyzing Suzuki-Miy aura coupling reaction by using the cellulose aerogel supported catalyst according to claim 1, wherein the method comprises the following steps: the mass fractions of the absolute ethyl alcohol, the glacial acetic acid and the methyltrimethoxysilane in the mixed solution are respectively as follows: 97wt% of absolute ethyl alcohol, 1wt% of glacial acetic acid and 1wt% of methyltrimethoxysilane.
5. The method for catalyzing Suzuki-Miy aura coupling reaction by using the cellulose aerogel supported catalyst according to claim 3, wherein the method comprises the following steps: in the step S3, the adding amount of the palladium acetate is 0.01-0.015 percent of the molar amount of the phenylboronic acid.
6. The method for catalyzing Suzuki-Miy aura coupling reaction by using the cellulose aerogel supported catalyst according to claim 1, wherein the method comprises the following steps: in the step S3, the modified cellulose aerogel accounts for 0.3-0.7 wt% of the mass fraction.
7. The method for catalyzing Suzuki-Miy aura coupling reaction by using the cellulose aerogel supported catalyst according to claim 1, wherein the method comprises the following steps: in step S3, the temperature of the low-temperature constant-temperature stirring reaction bath is set to be 20-25 ℃.
8. Application of modified cellulose aerogel supported palladium acetate in catalyzing Suzuki-Miyaura coupling reaction.
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