CN115463689B - Method for catalyzing Suzuki-Miyaura coupling reaction by using cellulose aerogel supported catalyst - Google Patents
Method for catalyzing Suzuki-Miyaura coupling reaction by using cellulose aerogel supported catalyst Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 title claims abstract description 40
- 239000001913 cellulose Substances 0.000 title claims abstract description 38
- 229920002678 cellulose Polymers 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 30
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 16
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 75
- 244000276331 Citrus maxima Species 0.000 claims description 29
- 235000001759 Citrus maxima Nutrition 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 17
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 15
- 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 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 5
- 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
- 238000001035 drying Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 10
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- DFPMSGMNTNDNHN-ZPHOTFPESA-N naringin Chemical class O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](OC=2C=C3O[C@@H](CC(=O)C3=C(O)C=2)C=2C=CC(O)=CC=2)O[C@H](CO)[C@@H](O)[C@@H]1O DFPMSGMNTNDNHN-ZPHOTFPESA-N 0.000 description 12
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 10
- 239000001606 7-[(2S,3R,4S,5S,6R)-4,5-dihydroxy-6-(hydroxymethyl)-3-[(2S,3R,4R,5R,6S)-3,4,5-trihydroxy-6-methyloxan-2-yl]oxyoxan-2-yl]oxy-5-hydroxy-2-(4-hydroxyphenyl)chroman-4-one Substances 0.000 description 9
- 229940052490 naringin Drugs 0.000 description 9
- 229930019673 naringin Natural products 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 5
- 125000006575 electron-withdrawing group Chemical group 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000004817 gas chromatography Methods 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
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- -1 sodium sulfide modified naringin Chemical class 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 group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 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
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012039 electrophile Substances 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
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 238000006276 transfer 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
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for catalyzing a Suzuki-Miyaura coupling reaction by a 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 the soaking is finished, washing the mixture to be neutral by distilled water, then replacing the mixture by tertiary butanol, standing the mixture at room temperature for 12 hours, putting the mixture into a refrigerator for freezing for 24 hours, taking the mixture out, putting the mixture into a freeze dryer, and taking the mixture out after freeze drying for 72 hours at 80 ℃ to obtain the modified cellulose aerogel. 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 multiple recycling of the palladium acetate catalyst, greatly reduces the test cost, and promotes the research and application of supported palladium acetate.
Description
Technical Field
The invention relates to the technical field of catalyst immobilization, in particular to a method for catalyzing a Suzuki-Miyaura coupling reaction by using a cellulose aerogel supported catalyst.
Background
At present, the Suzuki-Miyaura coupling reaction has the advantages of wide substrate application range, mild reaction conditions, stability to heat, air and water, most of byproducts are nontoxic, aftertreatment is easy to carry out and the like, and the Suzuki-Miyaura coupling reaction has extremely wide application in laboratory synthesis and industrial synthesis of organic fine products and medicaments.
The catalytic cycle process of the Suzuki-Miyaura coupling reaction generally comprises elementary reactions such as oxidation addition, metal transfer, reduction elimination and the like. The start of the catalytic cycle is that the organic electrophile and zero-valent palladium are subjected to oxidation addition reaction to generate R 1 Pd-X divalent palladium intermediate, then undergoes a metal transfer reaction with an organoboride to form R 1 -Pd-R 2 Intermediate, finally, coupling product R is obtained through reduction and elimination 1 -R 2 At the same time, the palladium in zero-valent state is released to participate in the catalytic cycle again.
However, during the palladium acetate catalyzed Suzuki-Miyaura coupling reaction, palladium black is easy to form, which not only affects the experiment, but also increases the palladium acetate consumption. Palladium acetate is expensive and a large amount of consumption increases the experimental cost.
The existing supported palladium acetate mostly uses silica gel, and the conversion rate of the supported palladium acetate for 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 a Suzuki-Miyaura coupling reaction by using a cellulose aerogel supported catalyst, which solves the problems of high palladium acetate consumption, high experimental cost and low supported palladium acetate conversion rate in the background art.
In order to achieve the above purpose, the invention provides a method for catalyzing a Suzuki-Miyaura coupling reaction by using a 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; washing with distilled water to neutrality after soaking, replacing with tert-butanol, standing at room temperature for 12 hr, freezing in refrigerator for 24 hr, taking out, freeze drying at 80deg.C for 72 hr, and taking out to obtain modified cellulose aerogel;
s3, palladium acetate fixation (catalyst Pd/M-GPA preparation): 5-10 mg of palladium acetate is dissolved in 5-15 mL of dichloromethane, the mixture is placed in a beaker, then 35-45 mg of modified cellulose aerogel is added, the beaker is sealed by a preservative film and then placed in a low-temperature constant-temperature stirring reaction bath, the rotation speed is fixed, the stirring is carried out for 16-24 h, and then the mixture is placed in room temperature and dried for 24h, thus obtaining the catalyst Pd/M-GPA.
Preferably, in step S1, the preparation process of the cellulose aerogel (GPA) is as follows: cutting fresh shaddock peel into cuboid blocks with proper size, placing the cuboid blocks in a beaker, sealing the cuboid blocks by using a preservative film, placing the cuboid blocks in a freeze dryer, freeze-drying the cuboid blocks at 80 ℃ for 4 days, and taking out the cuboid blocks to obtain the cellulose aerogel.
Preferably, the step of the Suzuki-Miyaura coupling reaction is as follows: sequentially adding aryl halide, phenylboric acid, potassium carbonate and Pd/M-GPA into paraxylene, and stirring and reacting for 20-60 minutes at 130-150 ℃ and 300R in an ambient atmosphere reflux atmosphere; after the reaction was completed (detected by TLC), the catalyst Pd/M-GPA was taken out; 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 the step S3, the addition amount of the palladium acetate is 0.01% -0.015% of the molar amount of the phenylboronic acid.
Preferably, in the step S3, the mass fraction of the modified naringin aerogel is 0.3-0.7wt%.
Preferably, in the step S3, the temperature of the low-temperature constant-temperature stirring reaction bath is set to be 20-25 ℃.
Therefore, the method for catalyzing the Suzuki-Miyaura a coupling reaction by using the cellulose aerogel supported catalyst ensures the yield of the Suzuki-Miyaura coupling reaction, realizes the multiple recycling of the palladium acetate catalyst, greatly reduces the test cost, and promotes the research and application of supported palladium acetate.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a scanning electron microscope image of different magnification factors of modified front and rear naringin aerogel in a method for catalyzing Suzuki-Miyaura coupling reaction by using a cellulose aerogel supported catalyst;
FIG. 2 is a scanning electron microscope image of modified front and rear shaddock ped aerogel adsorbed Pd (OAc) 2 at different magnifications in a method for catalyzing Suzuki-Miyaura coupling reaction by using a cellulose aerogel supported catalyst;
FIG. 3 is an XRD pattern of naringin cellulose aerogel before and after modification in a method of catalyzing Suzuki-Miyaura coupling reaction with a cellulose aerogel supported catalyst according to the invention;
FIG. 4 is an XRD pattern of palladium acetate adsorbed by naringin cellulose aerogel before and after modification in an embodiment of a method for catalyzing a Suzuki-Miyaura coupling reaction by using a cellulose aerogel supported catalyst;
FIG. 5 is a catalytic cycling test of the catalyst Pd/M-GPA-1 in a method of catalyzing a Suzuki-Miyaura coupling reaction with a cellulose aerogel supported catalyst according to the present invention.
Detailed Description
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1
A method for catalyzing a Suzuki-Miyaura coupling reaction by a cellulose aerogel supported catalyst, comprising the following steps:
s1, preparing shaddock ped aerogel (GPA): cutting fresh pericarpium Citri Grandis into rectangular blocks with a length of 2.5cm×2.8cm×1.8cm, placing in a 50mL plastic beaker, sealing with preservative film, freeze drying at 80deg.C for 4 days, and taking out to obtain pericarpium Citri Grandis aerogel;
s2, preparing modified shaddock ped aerogel (M-GPA): putting the shaddock ped aerogel obtained in the step S1 into a beaker containing 97mL of absolute ethyl alcohol, 1mL of glacial acetic acid and 1mL of methyltrimethoxysilane, and soaking for 9h at room temperature; washing with distilled water to neutrality after soaking, replacing with tert-butanol, standing at room temperature for 12 hr, freezing in refrigerator for 24 hr, taking out, freeze drying at 80deg.C for 72 hr, and taking out to obtain methyltrimethoxysilane modified pericarpium Citri Grandis aerogel (M-GPA-1);
s3, palladium acetate fixation (catalyst Pd/M-GPA preparation): dissolving 5mg of palladium acetate in 5mL of dichloromethane, placing in a 50mL beaker, adding 37mg of M-GPA, sealing the beaker by using a preservative film, placing in a low-temperature constant-temperature stirring reaction bath, setting the temperature of the low-temperature constant-temperature stirring reaction bath to 20 ℃, fixing the rotating speed, and stirring for 24 hours; then the mixture is dried for 24 hours at room temperature to obtain the catalyst Pd/M-GPA-1.
In the step S3, the addition amount of palladium acetate is 0.01-0.015% of the molar amount of phenylboronic acid in the Suzuki-Miyaura coupling reaction, and the mass fraction of the modified naringin aerogel is 0.3-0.7wt%.
Example two
As in example one, palladium acetate was supported on unmodified naringin aerogel to give Pd/GPA.
Example III
The sodium sulfide was used to modify the naringin aerogel under the same experimental conditions as in example one, and the specific steps are as follows:
on the basis of the shaddock ped aerogel obtained in the step S1, adding a sodium sulfide solution with the concentration of 1.5mol/L according to the ratio of shaddock ped aerogel to sodium sulfide solution=1:5, uniformly stirring by using a glass rod, standing at room temperature for 12h, washing to be neutral by using distilled water for multiple times, and detecting by using pH test paper.
After washing to neutrality, replacing with tert-butanol, standing at room temperature for 12h, freezing in refrigerator for 24h, taking out, freeze drying in a freeze dryer at 80deg.C for 72h, and taking out to obtain sodium sulfide modified naringin aerogel (M-GPA-2).
Then, according to the procedure of example S3, palladium acetate was supported on sodium sulfide-modified shaddock ped aerogel to obtain a catalyst Pd/M-GPA-2.
Example IV
The modification of the naringin aerogel with potassium hydroxide was carried out under the same experimental conditions as in example one, and the specific steps are as follows:
on the basis of the shaddock ped aerogel obtained in the step S1, KOH is used as an active agent, the shaddock ped aerogel and a potassium hydroxide (25%) solution are mixed according to the mass ratio of 1:3, soaked for 12 hours at room temperature, washed with distilled water for multiple times until the shaddock ped aerogel is neutral, and detected by using pH test paper.
After washing to neutrality, replacing with tert-butanol, standing at room temperature for 12h, freezing in a refrigerator for 24h, taking out, freeze-drying at 80deg.C for 72h, and taking out to obtain potassium hydroxide modified pericarpium Citri Grandis aerogel (M-GPA-3).
Then, according to the procedure of example S3, palladium acetate was supported on a potassium hydroxide-modified shaddock ped aerogel to obtain a catalyst Pd/M-GPA-3.
Example five
The modification of the naringin aerogel using dipotassium hydrogen phosphate was carried out under the same experimental conditions as in example one, and the specific steps are as follows:
based on the shaddock ped aerogel obtained in the step S1, K is used for 2 HPO 4 As an active agent, naringin aerogel and dipotassium hydrogen phosphate (25%) solution are mixed according to the mass ratio of 1:3, soaked for 12 hours at room temperature, washed with distilled water for many times to be neutral, and detected by using pH test paper.
After 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 a freeze dryer at 80deg.C for 72h, and taking out to obtain the naringin aerogel (M-GPA-4) modified with dipotassium hydrogen phosphate.
Then, according to the procedure of example S3, palladium acetate was supported on a potassium hydroxide-modified shaddock ped aerogel to obtain a catalyst Pd/M-GPA-4.
Experimental test
And (one) performing electron microscope scanning of different magnifications on the powdery samples of the shaddock ped aerogel and the modified shaddock ped aerogel. As shown in fig. 1, a and b are electron microscope images of modified pomelo peel aerogel; c is an electron microscope image of the methyltrimethoxysilane modified shaddock ped aerogel; d is a partial enlarged view of figure c; e. f is a sodium sulfide modified shaddock ped aerogel electron microscope image; g is an electron microscope image of potassium hydroxide modified shaddock ped aerogel; h is a partial enlarged view of the graph g; i is an electron microscope image of dipotassium hydrogen phosphate modified shaddock ped aerogel; j is a partial enlarged view of figure i.
The result shows that the modified pomelo peel aerogel has a honeycomb porous structure, a large number of micro-pore channels are formed, the internal pore shapes are different in multiple rows, the layered structures are closely arranged, and the honeycomb structure is loose. The modified shaddock ped aerogel surface shows a 3D interconnected porous structure, has a plurality of small holes uniformly distributed, and shows an irregularly-shaped plant flake structure. Each porous structure is loosely filled with open spaces. The modification effect of the modifier on the shaddock ped aerogel in the embodiment is proved to be better.
And (II) testing the catalyst Pd/GPA and Pd/M-GPA respectively by using a scanning electron microscope. As shown in fig. 2, a and b are SEM images of Pd/GPA; c. d is SEM image of Pd/M-GPA-1; e. f is SEM image of Pd/M-GPA-2; g. h is SEM image of Pd/M-GPA-3; i. j is SEM image of Pd/M-GPA-4.
Compared with the scanning electron microscope image of FIG. 1, which does not adsorb palladium acetate, palladium acetate is loaded on the shaddock ped aerogel and the modified shaddock Pi Qining gel, after catalysts Pd/GPA and Pd/M-GPA are generated, the shapes of the catalysts Pd/GPA and Pd/M-GPA and GPA are hardly changed obviously, and the catalyst is still in a three-dimensional netlike porous space structure and has a plant flake structure with a regular shape. The catalyst has the advantages that the original morphology structure of the carrier GPA and the carrier M-GPA is still maintained after palladium acetate is loaded to generate the catalyst.
(III) XRD pattern examination is carried out on the shaddock ped aerogel and the modified shaddock ped aerogel, and the catalysts Pd/GPA and Pd/M-GPA respectively, as shown in fig. 3 and 4.
From the figure, it can be seen that the diffraction peaks of the carrier GPA and M-GPA and the catalyst Pd/GPA and Pd/M-GPA are consistent, which indicates that the crystal structures of the GPA and M-GPA are not destroyed after the palladium acetate and GPA coordinate with the M-GPA. The characteristic diffraction peak newly generated by Pd/GPA at 2θ=38.78° is the (111) crystal plane of Pd (II), and the characteristic diffraction peak newly generated by Pd/M-GPA at 2θ=39.06° is the (111) crystal plane of Pd (II). Thus, it was further shown that palladium acetate had been attached to the naringin aerogel before and after modification, resulting in catalysts Pd/GPA and Pd/M-GPA.
(IV) the Pd/GPA and Pd/M-GPA catalysts are respectively put into a Suzuki coupling reaction taking bromobenzene (39 mg,0.25 mmol) and phenylboronic acid (61 mg,0.5 mmol) as reactants, and the yield is calculated by Gas Chromatography (GC) analysis, so as to obtain the catalyst for the optimal reaction.
The Suzuki-Miyaura coupling reaction experimental steps are as follows: sequentially adding aryl halide, phenylboric acid, potassium carbonate and Pd/M-GPA into paraxylene, and stirring and reacting for 20-60 minutes at 130-150 ℃ in the reflux atmosphere of the environment atmosphere; after the reaction was completed (detected by TLC), the catalyst Pd/M-GPA was taken out; 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 during this procedure, and the results are shown in Table 1.
TABLE 1 selection of catalysts in Suzuki coupling reactions
As can be seen from Table 1, the catalyst Pd/M-GPA-1 has the best effect on the Suzuki coupling reaction, and provides the cross-coupled product in excellent yield (96%), which proves that the methyltrimethoxysilane modified naringin aerogel supported catalyst in the embodiment I has the best effect.
(V) using Pd/M-GPA-1 prepared in example I as catalyst, using Suzuki-Miyaura coupling reaction of bromobenzene and phenylboronic acid as model reaction, expanding reactant substrate, and using K 2 CO 3 And paraxylene as a base and solvent examined the activity of the catalyst.
The Suzuki-Miyaura coupling reaction was carried out as follows, in which Pd/M-GPA-1 was used as a catalyst, and the results are shown in Table 2.
TABLE 2 catalytic Activity test of Pd/M-GPA-1 in Suzuki-Miyaura coupling reactions
| 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 catalyst Pd/M-GPA-1 when catalyzing the Suzuki-Miyaura coupling reaction, the substituted functional groups of the aryl halides have an effect on the rate of the coupling reaction, the difficulty order of the reaction is RI > RBr (Entry 1-2), and the cross-coupled products are provided in excellent yields (96-97%). The electron effect of different substituents of aryl bromides is explored, and cross-coupling products are obtained in excellent yields (91-96%) in the presence of electron withdrawing groups such as fluorine, chlorine, nitro and trifluoromethoxy (Entry 3-6), which indicate that coupling reaction is facilitated when electron withdrawing groups are attached to benzene rings of bromobenzene compounds as substrates.
Wherein, the yield of the coupling product obtained by Suzuki-Miyaura coupling reaction of bromoarene with electron withdrawing group (-CN) is lower than that of other electron withdrawing groups, because the positioning effect of electron withdrawing group in 4-bromobenzonitrile is meta-position of benzene ring, -CN and benzene ring have a-CH between them 2 Thus the locating group is in fact-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 rings. The result shows that the catalyst Pd/M-GPA-1 has high catalytic activity in the catalytic Suzuki-Miyaura coupling reaction.
Catalyst Pd/M-GPA-1 catalyst cycle test.
The reaction mixture was stirred at 140℃for 20 minutes using bromobenzene (39 mg,0.25 mmol), phenylboronic acid (61 mg,0.5 mmol), potassium carbonate (138 mg,1.0 mmol), pd/M-GPA-1 (35 mg,1.0 mol%) and 4mL p-xylene at reflux under ambient atmosphere. After the reaction, the catalyst Pd/M-GPA-1 was taken out, washed with ethyl acetate, extracted, and the recovered catalyst was dried at room temperature for 24 hours, and then used as it is. 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. Wherein bromobenzene can be replaced by other reactant substrates for catalytic cycle experiments.
The results of the catalytic cycle experiments performed on the different reactant substrates are shown in fig. 5, wherein 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 in the catalytic process is obviously reduced after 3-4 times of continuous recycling. The activity of the common palladium catalyst is extremely fast in the use process, and the common palladium catalyst needs to be activated again after being used once to participate in the reaction.
The reason for the decrease in catalytic activity of catalyst Pd/M-GPA-1 in this experiment is: the halogenated aromatic hydrocarbon of the Suzuki-Miyaura coupling reaction firstly interacts with the catalyst, the halogenated aromatic hydrocarbon can be adsorbed on active sites on the surfaces of the nano particles, the active sites are mainly at the edge points and the top points of the nano particles, and the adsorption performance of the sites is the lowest. And secondly, the agglomeration and dissociation of the palladium nano catalyst also have a certain influence on the catalytic activity of the catalyst, when the nano palladium particles are heated, catalyst palladium atoms on the surfaces are separated from the particles and enter solution free palladium atoms to perform a catalytic action, meanwhile, the free palladium atoms in the solution are agglomerated again to the surfaces of the palladium particles to form dynamic balance, the agglomeration phenomenon of the nano palladium is promoted by the increase of the environmental temperature, the nano palladium particles with large particles are generated, the catalytic activity is reduced, and even palladium black is generated to be deactivated.
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 multiple recycling of the palladium acetate catalyst, greatly reduces the test cost, and promotes the research and application of supported palladium acetate.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (4)
1. A method for catalyzing Suzuki-Miyaura coupling reaction by using a cellulose aerogel supported catalyst is characterized by comprising the following steps of: the method comprises the following steps:
s1, preparing cellulose aerogel GPA: cutting fresh shaddock peel into cuboid blocks with proper size, placing the cuboid blocks in a beaker, sealing the cuboid blocks by using a preservative film, placing the cuboid blocks in a freeze dryer, freeze-drying the cuboid blocks at 80 ℃ for 4 days, and taking out the cuboid blocks to obtain cellulose aerogel;
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; washing with distilled water to neutrality after soaking, replacing with tert-butanol, standing at room temperature for 12 hr, freezing in refrigerator for 24 hr, taking out, freeze drying at 80deg.C for 72 hr, and taking out to obtain modified cellulose aerogel;
s3, preparing a catalyst Pd/M-GPA: dissolving 5-10 mg of palladium acetate in 5-15 mL of dichloromethane, placing the solution in a beaker, then 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 and drying for 24h to obtain a catalyst Pd/M-GPA;
Suzuki-Miyaura coupling reaction: sequentially adding aryl halide, phenylboric acid, potassium carbonate and catalyst Pd/M-GPA into paraxylene, and stirring and reacting for 20-60 minutes at 130-150 ℃ in the ambient atmosphere reflux atmosphere.
2. The method for catalyzing a Suzuki-Miy aura coupling reaction by using a 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.
3. The method for catalyzing a Suzuki-Miy aura coupling reaction by using a cellulose aerogel supported catalyst according to claim 1, wherein the method comprises the following steps: in the step S3, the addition amount of the palladium acetate is 0.01-0.015% of the molar amount of phenylboronic acid participating in the Suzuki-Miyaura coupling reaction.
4. The method for catalyzing a Suzuki-Miy aura coupling reaction by using a cellulose aerogel supported catalyst according to claim 1, wherein the method comprises the following steps: in the step S3, the temperature of the low-temperature constant-temperature stirring reaction bath is set to be 20-25 ℃.
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