CN116747878B - Magnetic nano microsphere and preparation method and application thereof - Google Patents
Magnetic nano microsphere and preparation method and application thereof Download PDFInfo
- Publication number
- CN116747878B CN116747878B CN202311029566.2A CN202311029566A CN116747878B CN 116747878 B CN116747878 B CN 116747878B CN 202311029566 A CN202311029566 A CN 202311029566A CN 116747878 B CN116747878 B CN 116747878B
- Authority
- CN
- China
- Prior art keywords
- nhco
- magnetic
- catalyst
- reaction
- cooh
- 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
- 239000004005 microsphere Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 4
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- -1 -NHCO-Ph Chemical group 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali 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 5
- 239000002904 solvent Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 230000036571 hydration Effects 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000005932 reductive alkylation reaction Methods 0.000 claims 1
- 150000001540 azides Chemical class 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000002296 dynamic light scattering Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000011943 nanocatalyst Substances 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- SXLHAMYMTUEALX-UHFFFAOYSA-N (4-methoxyphenoxy)boronic acid Chemical compound COC1=CC=C(OB(O)O)C=C1 SXLHAMYMTUEALX-UHFFFAOYSA-N 0.000 description 2
- FWMBBQJILJGRRI-UHFFFAOYSA-N 3-azidopropylbenzene Chemical compound [N-]=[N+]=NCCCC1=CC=CC=C1 FWMBBQJILJGRRI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HJQRKTUTZLWNDD-UHFFFAOYSA-N CCOC(OCC)(OCC)CCN[SiH3] Chemical compound CCOC(OCC)(OCC)CCN[SiH3] HJQRKTUTZLWNDD-UHFFFAOYSA-N 0.000 description 2
- 101100184487 Caenorhabditis elegans mnp-1 gene Proteins 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000005046 dihydronaphthyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LVIBVJFXXPEGBO-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)benzamide Chemical compound CCO[Si](OCC)(OCC)CCCNC(=O)C1=CC=CC=C1 LVIBVJFXXPEGBO-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/42—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitrogen-to-nitrogen bonds
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a magnetic nano microsphere, a preparation method and application thereof, wherein the magnetic nano microsphere uses Fe 3 O 4 Denoted by @ Pd @ Si-R', which has a core-shell structure, expressed as Fe 3 O 4 Pd is supported on the core as a core, and modified silicon compounds Si-R' are used as shells. The application provides a magnetic nano microsphere which can realize the catalytic effect of high-efficiency separation and recovery. The catalyst is used for the reaction process of preparing N-ethylaniline by catalyzing nitrobenzene to reduce and alkylate and preparing primary amine by azide reduction in a Suzuki reaction, and realizes the multiple recovery of the catalyst. Meanwhile, the magnetic full-automatic organic synthesis is realized.
Description
Technical Field
The application belongs to the field of magnetic materials, and particularly relates to a magnetic nanoparticle, a preparation method and application thereof.
Background
The magnetic nano catalyst has wide application in organic synthesis catalytic reaction, and the excellent dispersibility and easy separation capability enable the magnetic nano catalyst to be between homogeneous phase and heterogeneous phase boundaries, and the size and the surface property enable the magnetic nano catalyst to show unique catalytic performance.
In the prior art, fe 3 O 4 @Pd (Mag-Core) or Fe 3 O 4 @SiO 2 The magnetic nano catalyst in the form of Pd (Mag-Shell-Core) is reacted under magnetic stirring, and the magnetic nano catalyst is difficult to recycle.
Disclosure of Invention
In order to solve the technical problems, the application provides a magnetic nano microsphere which uses Fe 3 O 4 Denoted by @ Pd @ Si-R', which has a core-shell structure, expressed as Fe 3 O 4 Pd is loaded on the core and takes a modified silicon compound Si-R' as a shell;
wherein R' is selected from the group consisting of-C 1-12 Alkyl, -C 6-20 Aryl, -NHCO-C 6-20 Aryl, - (CH) 2 ) n -COOH、-(CH 2 ) n -CN、-(CH 2 ) n -Cl、-(CH 2 ) n -NR 1 R 2 、-(CH 2 ) n -NHCO-(CH 2 ) n -COOH、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-(CH 2 ) n -OH;
Wherein n is the same or different and is an integer selected from 0 to 10 independently of each other;
R 1 and R is 2 Identical or different, independently of one another, from H, C 1-12 An alkyl group.
According to an embodiment of the application, n is identical or different and is independently an integer from 0 to 6.
According to an embodiment of the application, R' is selected from-C 1-10 Alkyl, -C 6-14 Aryl, -NHCO-C 6-14 Aryl, - (CH) 2 ) n -COOH、-(CH 2 ) n -CN、-(CH 2 ) n -Cl、-(CH 2 ) n -NR 1 R 2 、-(CH 2 ) n -NHCO-(CH 2 ) n -COOH、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-(CH 2 ) n -OH。
According to an embodiment of the application, R' is selected from propyl, - (CH) 2 ) 3 - NHCO-(CH 2 ) 2 -COOH, carboxyl, -NHCO-Ph, pentyl, octyl, decyl, phenyl, -CH 2 -Ph-、-(CH 2 ) 2 -CN、-(CH 2 ) 3 -Cl、-(CH 2 ) 3 -NH 2 、-(CH 2 ) 3 -NEt 2 、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-(CH 2 ) 2 -COOH、-NHCO-(CH 2 ) 4 -COOH、-NHCO-Ph、-NHCO-(CH 2 ) 2 -OH。
According to an embodiment of the application, the Fe 3 O 4 The particle size of (2) is 50nm to 300nm, and exemplary are 50nm, 100nm, 125nm, 150nm, 200nm, 250nm, 300nm.
According to an embodiment of the application, the loading of Pd is 1-15 wt%, such as 1wt%, 3wt%, 5wt%, 7wt%, 9wt%, 10wt%, 12wt%, 15wt% based on the mass of the magnetic nanoparticle.
According to an embodiment of the application, the thickness of the shell is 10-300 a nm a.
According to an embodiment of the application, the shell is 100% coated.
According to an embodiment of the present application, the magnetic nanoparticle has a hydrated particle size of 100 to 1100nm, preferably 200 to 1000nm, and more preferably 450 to 800nm.
The application also provides a preparation method of the magnetic nano microsphere, which comprises the following steps:
fe is added to 3 O 4 @Pd magnetic nanoparticles and modified silicon compounds (RO) 3 Si-R' is mixed in a solventThe magnetic nanometer microsphere is prepared through a combination reaction,
wherein R' has the meaning as above, R is selected from C 1-12 An alkyl group.
According to an embodiment of the application, an alkaline solution is also added to the process to adjust the pH to a pH of 7-12.
According to an embodiment of the present application, the alkali solution is selected from at least one of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. In the present application, the concentration and content of the alkali solution are not particularly limited, so that the pH of the system is 7 to 12.
According to an embodiment of the present application, the solvent is selected from at least one of water, ethanol, ethylene glycol dimethyl ether, and the like. Preferably a mixture of water and ethanol.
According to an embodiment of the application, the Fe 3 O 4 @Pd magnetic nanoparticles and modified silicon compounds (RO) 3 The mass ratio of Si to R' is 0.05-1:1, preferably 0.2-0.6:1.
According to an embodiment of the application, the Fe 3 O 4 The mass volume ratio of the@Pd magnetic nano-particles to the solvent is 1-10 (mg): 1 (mL), preferably 1-6 (mg): 1 (mL).
According to an embodiment of the application, the temperature of the reaction is 30-90 ℃, preferably 40-80 ℃.
According to an embodiment of the application, the reaction time is 0.5-10h, preferably 1-8h.
According to an embodiment of the application, the Fe 3 O 4 The preparation method of the Pd magnetic nano-particles is a conventional technology in the field. Illustratively, the Fe 3 O 4 The preparation method of the@Pd magnetic nanoparticle comprises the following steps:
metal palladium salt and Fe 3 O 4 Mixing in water, reacting at room temperature, adding a reducing agent, and reacting overnight to obtain the Fe 3 O 4 @pd magnetic nanoparticles.
Preferably, the metallic palladium salt is, for example, sodium chloropalladate.
Also exemplary, the Fe 3 O 4 The preparation method of the@Pd magnetic nanoparticle comprises the following steps: metal palladium salt and Fe 3 O 4 Dispersing magnetic nano particles with water, regulating pH of the system with alkali solution, reacting at room temperature, adding a reducing agent under cooling with ice water bath, stirring overnight, magnetically separating, and washing with water for 3 times to obtain Fe 3 O 4 @Pd。
As an exemplary embodiment of the present application, the magnetic nanoparticle is prepared as follows: fe is added to 3 O 4 @Pd magnetic nanoparticles and modified silicon compounds (RO) 3 Dispersing Si-R' in a mixed solution of water and alcohol, regulating the pH of the system by using alkali solution, reacting at room temperature, magnetically separating, and washing for 3 times to obtain the magnetic nano microsphere Fe 3 O 4 @Pd@Si-R’。
The application also provides application of the magnetic nano microsphere as a transition metal Pd catalyst, and the application is exemplified by a Pd catalyst-catalyzed coupling reaction (such as a C-C bond coupling reaction and a C-N bond coupling reaction), a Pd catalyst-catalyzed reduction reaction and the like, for example, the magnetic nano microsphere is used as a catalyst for a Suzuki reaction, is used for catalyzing nitrobenzene to prepare aniline, N-alkylaniline and/or N, N-dialkylaniline by reduction alkylation, and is used for catalyzing azide compounds to reduce primary amines. Preferably as a magnetic catalyst for high throughput automated organic synthesis reactions.
The beneficial effects of the application are that
The application provides a magnetic nano microsphere which can realize the catalytic effect of high-efficiency separation and recovery. The catalyst is used for the reaction process of preparing aniline, N-alkylaniline and N, N-dialkylaniline by catalyzing reduction alkylation of nitrobenzene and preparing primary amine by azide reduction, and realizes multiple recovery of the catalyst. Meanwhile, high-flux automatic organic synthesis is realized.
The term "C 1-12 Alkyl "denotes straight-chain and branched alkyl having 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms," C 1-6 Alkyl "means straight and branched alkyl groups having 1,2, 3, 4, 5 or 6 carbon atoms. The alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylAnd (c) a cyclobutyl group, 1-methylbutyl group, 1-ethylpropyl group, 1, 2-dimethylpropyl group, neopentyl group, 1-dimethylpropyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 2-ethylbutyl group, 1-ethylbutyl group, 3-dimethylbutyl group, 2-dimethylbutyl group, 1-dimethylbutyl group, 2, 3-dimethylbutyl group, 1, 3-dimethylbutyl group or 1, 2-dimethylbutyl group, or the like, or an isomer thereof.
The term "C 6-20 Aryl "is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring, preferably" C ", of monovalent aromatic or partly aromatic nature having 6 to 20 carbon atoms 6-14 Aryl group). The term "C 6-14 Aryl "is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring (" C ") having a monovalent aromatic or partially aromatic character of 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms 6-14 Aryl), in particular a ring having 6 carbon atoms ("C) 6 Aryl "), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 Aryl "), e.g. indanyl or indenyl, or a ring having 10 carbon atoms (" C 10 Aryl "), such as tetralin, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms (" C " 13 Aryl "), e.g. fluorenyl, or a ring having 14 carbon atoms (" C) 14 Aryl "), such as anthracenyl. When said C 6-20 When the aryl group is bonded to another group, the bonding position may be a phenyl group or a group bonded to a phenyl group.
Drawings
FIG. 1 is a flow chart of the preparation of the magnetic nanoparticle of the present application.
FIG. 2 is a graph showing the yields of the products produced by the catalytic reactions performed multiple times on the catalyst after the separation and recovery reactions of comparative application examples 2 and 4 and application example 31.
Fig. 3a is a schematic and actual view showing the reaction formula and the reaction result in the automated azide reduction reaction in application example 47, and fig. 3b is a schematic and actual view showing the process of the automated azide reduction reaction in application example 47.
Detailed Description
The technical scheme of the application will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Fe 3 O 4 The specific scheme for the synthesis of @ Pd @ PTEO (i.e., MNP-01) is shown below:
the first step: 1 mmol of sodium chloropalladate and 1 g of Fe are added to 50 mL of water 3 O 4 After stirring the magnetic nanoparticles (200 nm) at room temperature for 1 h, the system pH was adjusted to 12 with 1M NaOH aqueous solution. Reaction 6 h was sonicated and mechanically stirred. 1 mmol of sodium borohydride was added under cooling in an ice-water bath, and the reaction was stirred overnight. Finally, fe is prepared 3 O 4 Magnetic attraction separation is carried out on the Pd magnetic nano-particles, and the nano-particles are washed for 3 times. XPS detects Pd content of 5wt%.
And a second step of: 500 mg of Fe is added into a 500 mL three-neck round bottom flask 3 O 4 The @ Pd magnetic nanoparticles were dispersed with 100 mL water and 200 mL ethanol and the system was basicity adjusted by adding 5 mL ammonia. 2 g triethoxypropyl silane was added and reacted overnight with mechanical stirring. Fe obtained 3 O 4 Magnetic attraction separation is carried out on the magnetic nano particles @ Pd @ PTEO and ethanol washing is carried out for 3 times. XPS detects Fe 3 O 4 Pd content in @ Pd @ PTEO is 3 wt%.
Example 2
Fe 3 O 4 The specific synthesis scheme of @ Pd @ APTES (MNP-09) is as follows:
the first step: the same as in example 1, first step
And a second step of: 500 mg of Fe is added into a 500 mL three-neck round bottom flask 3 O 4 The @ Pd magnetic nanoparticles were dispersed with 100 mL water and 250 mL ethanol and the system was basicity adjusted by adding 5 mL ammonia. Adding 2 g triethoxypropylamino silane, reacting 12 h under mechanical stirring, magnetically separating the obtained product, and washing with ethanol for 3 times to obtain Fe 3 O 4 @Pd@APTES。
Example 3
Fe 3 O 4 The specific scheme for the synthesis of @ Pd @ Si-COOH (MNP-12) is shown below:
into a 250 mL three neck round bottom flask was charged 500 mg of Fe prepared in example 2 3 O 4 @Pd@APTES was dispersed with 100 mL of DMF, succinic anhydride (1.1 equiv) was added dropwise, and then reacted by heating at 60℃under stirring 2 h. Fe obtained 3 O 4 Magnetic attraction separation is carried out on the magnetic nano particles of@Pd@Si-COOH, and the magnetic nano particles are washed 3 times.
Example 4
Fe 3 O 4 The specific synthetic procedure for the @ Pd @ Si-NHCO-Ph (i.e., MNP-14) is as follows:
the first step: 5 mmol of triethoxypropylaminosilane and EDCI (1.0 equiv.) are placed in a 50 mL round bottom flask and dispersed with 10 mL dichloromethane, 5 mmol of benzoic acid are added dropwise with stirring and cooling in an ice water bath, after reaction 2 h at room temperature, after extraction of the system 3 times with 10 mL water, the organic phase is collected and dried by spinning to give N- (3- (triethoxysilyl) propyl) benzamide.
And a second step of: the same as in preparation example 1
And a third step of: 500 mg of Fe is added into a 500 mL three-neck round bottom flask 3 O 4 The @ Pd magnetic nanoparticles were dispersed with 100 mL water and 250 mL ethanol and the system was basicity adjusted by adding 5 mL ammonia. Adding 2 g modified silane raw material, reacting 12 h under mechanical stirring, magnetically separating the prepared product, and washing with water for 3 times to obtainFe 3 O 4 @Pd@Si-NHCO-Ph。
Examples 5 to 13
Examples 5-13 differ from example 1 in that the propyl group of example 1 was replaced with R' in Table 1 below.
Example 14
Example 14 differs from example 2 in that R 'in Table 1 is used instead of R' in example 1.
Example 15
Example 15 differs from example 3 in that R 'in Table 1 is used instead of R' in example 1.
TABLE 1 hydration particle size table of magnetic nanoparticle prepared with each R' group in examples 1 to 15
In the table 1, the contents of the components,
[a] dynamic Light Scattering (DLS) test
Examples 16 to 18
Examples 16 to 18 differ from example 1 in that Fe is used 3 O 4 The particle sizes of the obtained products were 50nm, 125nm and 300nm, respectively, and the hydrated particle sizes of the obtained products are shown in Table 2 below.
TABLE 2 hydrated particle size of magnetic nanoparticle of examples 1, 16-18
Magnetic bead numbering | Fe 3 O 4 Size (nm) | Particle size of hydration (nm) [a] | |
Example 1 | MNP-1 | 200 | 475.45 |
Example 16 | MNP-16 | 50 | 213.47 |
Example 17 | MNP-17 | 125 | 357.83 |
Example 18 | MNP-18 | 300 | 768.25 |
[a] Dynamic Light Scattering (DLS) test
Examples 19 to 21
Examples 19-21 differ from example 1 in that the molar ratio of sodium chloropalladate to sodium borohydride used was 0.3 mmol,1 mmol,2 mmol, respectively, and the hydrated particle size of the resulting product is shown in Table 3 below.
TABLE 3 hydrated particle size of each magnetic nanoparticle of examples 1 and 19-21
Magnetic bead numbering | Pd loading (wt%) [b] | Particle size of hydration (nm) [a] | |
Example 1 | MNP-1 | 3 | 475.45 |
Example 19 | MNP-19 | 1 | 482.56 |
Example 20 | MNP-20 | 10 | 553.18 |
Example 21 | MNP-21 | 15 | 658.51 |
[a] Dynamic Light Scattering (DLS) test; [b] x-ray photoelectron spectroscopy (XPS) test
In the table, the Pd loading is based on the mass of the magnetic nanoparticle.
Application examples 1-15 catalytic Suzuki coupling reactions
To a reaction flask of 10 mL were added 3 mol% (relative to bromobenzene) of the magnetic nanoparticle catalyst of examples 1-15 and 10 mol% (relative to bromobenzene) of the ligand triphenylphosphine, respectively, and 2 mL of 1, 4-dioxane was added for dispersion. 0.1 mmol of bromobenzene and cesium carbonate (the content of cesium carbonate is 1.5 times that of bromobenzene) are added under the protection of nitrogen, and p-methoxyphenylboric acid (the content of p-methoxyphenylboric acid is 1.1 times that of bromobenzene) is added under stirring, and the mixture is heated to 70 ℃ for reaction for 8 hours. After TLC detection of the reaction results, 20. Mu.l of the system was taken, ethyl acetate was diluted to 1 mL, and GC-MS detection was performed to obtain the yield.
The specific process is as follows:
TABLE 4 yields of the products in application examples 1-15
Application examples 16-30 catalytic reduction alkylation of nitrobenzene to prepare aniline, N-ethylaniline and N, N-diethylaniline
To a 25 mL reaction flask was added 3 mol% (relative to nitrobenzene) of the magnetic nanoparticle catalyst of examples 1-15, respectively, and dispersed with 5 mL ethanol. 0.1 mmol of nitrobenzene was added and the reaction was carried out at room temperature under hydrogen. After TLC detection of the reaction results, 20. Mu.l of the system was taken, ethyl acetate was diluted to 1 mL, and GC-MS detection was performed to obtain the yield.
The specific process is as follows:
TABLE 4 yields of the products in application examples 16-30
In Table 4, comparative application example 1 was conducted in the same manner as in application example 15 using Pd/C as a catalyst.
Application examples 31-45 catalytic reduction of azides to primary amines
To a reaction flask of 10 mL was added 0.5 mol% of the magnetic nanoparticle catalyst of examples 1-15, respectively, and 1 mL ethanol was added for dispersion. 0.015 mmol of phenylpropyl azide was added, hydrazine hydrate (2 times the content of phenylpropyl azide) was added with stirring, and the mixture was heated to 40℃for 45 min. After TLC detection of the reaction results, 20. Mu.l of the system was taken, ethyl acetate was diluted to 1 mL, and GC-MS detection was performed to obtain the yield.
The specific process is as follows:
TABLE 5 yields of the products in application examples 31-45
In Table 5, comparative application examples 2 to 5 were each carried out as Pd/C, fe 3 O 4 、Fe 3 O 4 @Pd、Fe 3 O 4 @Pd@SiO 2 The rest of the procedure was the same as in application example 31, except that it was catalyst.
Application example 46
Recovery experiments:
comparative examples 2, 4 and 31 were separated backThe catalyst after the reaction (Pd/C, fe respectively) 3 O 4 @Pd,Fe 3 O 4 @Pd@PTEO), the reaction was continued according to application example 31 after washing 3 times with ethanol, a plurality of recovery reactions were achieved, and the yield was calculated for the produced product, and the experimental results are shown in FIG. 2. As can be seen from FIG. 2, the Pd/C is lost in productivity after the third reaction cycle, and the catalyst Pd/C, fe after the fourth reaction cycle 3 O 4 The catalyst activity of @ Pd is obviously reduced, and Fe 3 O 4 The shell layer of the application can realize the protection of the catalytic active substance transition metal palladium.
Application example 47 automated azide reduction reaction
Fig. 3a is a schematic and actual view showing the reaction formula and the reaction result in the automated azide reduction reaction in application example 47, and fig. 3b is a schematic and actual view showing the process of the automated azide reduction reaction in application example 47.
In FIG. 3a or FIG. 3b, R 1 Represents hydrazine hydrate, R 2 Represents an azide compound, C represents a catalyst, and P represents a prepared product.
The first step: and (5) prefabricating the plate. In a 96-well reaction plate, 20 microliters of hydrazine hydrate and 300 microliters of ethanol are preloaded per well; a96-well magnetic catalyst plate was preloaded with 600. Mu.l of the catalyst Fe of example 1 3 O 4 @Pd@PTEO ethanol solution (4 mg/mL) per well; in a 96-well recovery plate, 800 microliters of ethanol per well were preloaded.
And a second step of: and (5) transferring liquid. The pipetting is set at 300 microliters. 48 azide (specific azide is shown in Table 6 below) in ethanol (2 mL 1 mol/L) was transferred to a reaction plate 96 well (48X 2)
And a third step of: magnetic solid transfer. The magnetic rod (containing the magnetic rod sleeve) is arranged in the magnetic catalyst plate, the magnetic attraction is 30 and s, the magnetic rod (containing the magnetic rod sleeve) is put forward and then is transferred into the reaction plate, only the magnetic rod is moved out, and the magnetic catalyst is dispersed in the reaction liquid by the magnetic rod sleeve.
Fourth step: the reaction was slapped. Setting the reaction temperature at 40 ℃ and the reaction time at 30 min. The magnetic rod sleeve is vertically flapped up and down, and the reaction solution is fully and uniformly mixed.
Fifth step: and (5) magnetic attraction separation. After the reaction, the catalyst is moved into a magnetic rod, the magnetic rod (containing a magnetic rod sleeve) is arranged in a reaction plate, the magnetic attraction is 30 s, the magnetic rod (containing the magnetic rod sleeve) is lifted and then is transferred into a recovery plate, the magnetic rod (containing the magnetic rod sleeve) is moved out, and the catalyst is dispersed in the recovery liquid. And (3) separating the reaction system from the catalyst.
Sixth step: and (5) analyzing results. The reaction plate was removed, 20. Mu.l of each well was taken, diluted to 1.1 mL with ethyl acetate, and the reaction was analyzed by GC-MS.
Table 6 shows the catalyst Fe in example 1 3 O 4 Yield of product prepared by automated catalytic azide reduction reaction of @ pd @ pteo.
Table 6: yield table of catalyst automated catalytic azide reduction reaction product in example 1
/>
/>
The embodiments of the present application have been described above by way of example. However, the scope of the present application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art, which fall within the spirit and principles of the present application, are intended to be included within the scope of the present application.
Claims (10)
1. A magnetic nano microsphere is characterized in that Fe is used as the magnetic nano microsphere 3 O 4 @Pd@Si-R' represents,it has a core-shell structure, with Fe 3 O 4 Pd is loaded on the core and takes a modified silicon compound Si-R' as a shell;
wherein R' is selected from the group consisting of-C 1-12 Alkyl, -C 6-20 Aryl, -NHCO-C 6-20 Aryl, - (CH) 2 ) n -COOH、-(CH 2 ) n -CN、-(CH 2 ) n -Cl、-(CH 2 ) n -NR 1 R 2 、-(CH 2 ) n -NHCO-(CH 2 ) n -COOH、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-(CH 2 ) n -OH;
Wherein n is the same or different and is an integer selected from 0 to 10 independently of each other;
R 1 and R is 2 Identical or different, independently of one another, from H, C 1-12 An alkyl group.
2. Microsphere according to claim 1, characterized in that R' is selected from-C 1-10 Alkyl, -C 6-14 Aryl, -NHCO-C 6-14 Aryl, - (CH) 2 ) n -COOH、-(CH 2 ) n -CN、-(CH 2 ) n -Cl、-(CH 2 ) n -NR 1 R 2 、-(CH 2 ) n -NHCO-(CH 2 ) n -COOH、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-(CH 2 ) n -OH。
3. The microsphere of claim 1, wherein R' is selected from the group consisting of propyl, - (CH) 2 ) 3 - NHCO-(CH 2 ) 2 -COOH, carboxyl, -NHCO-Ph, pentyl, octyl, decyl, phenyl, -CH 2 -Ph-、-(CH 2 ) 2 -CN、-(CH 2 ) 3 -Cl、-(CH 2 ) 3 -NH 2 、-(CH 2 ) 3 -NEt 2 、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-(CH 2 ) 2 -COOH、-NHCO-(CH 2 ) 4 -COOH、-NHCO-Ph、-NHCO-(CH 2 ) 2 -OH;
The Fe is 3 O 4 The particle size of (2) is 50nm-300nm;
based on the mass of the magnetic nano microsphere, the load of Pd is 1-15 wt%.
4. The microsphere of claim 1, wherein the shell has a thickness of 10 to 300 a nm; the shell is 100% coated;
the hydration particle size of the magnetic nano microsphere is 100-1100nm.
5. A method of preparing microspheres according to any one of claims 1-4, wherein the method comprises:
fe is added to 3 O 4 @Pd magnetic nanoparticles and modified silicon compounds (RO) 3 Si-R' is mixed and reacted in a solvent to prepare the magnetic nano microsphere,
wherein R' has the meaning as above, R is selected from C 1-12 An alkyl group.
6. The method according to claim 5, wherein the method is further characterized by adding an alkali solution to adjust the pH to 7-12;
the alkali solution is at least one selected from ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
7. The method of claim 5, wherein the solvent is selected from at least one of water, ethanol, ethylene glycol dimethyl ether.
8. The method according to claim 5, wherein the Fe 3 O 4 @Pd magnetic nanoparticles and modified silicon compounds (RO) 3 The mass ratio of Si-R' is 0.05-1:1;
the Fe is 3 O 4 @Pd magnetThe mass volume ratio of the sex nanoparticle to the solvent is 1-10 (mg): 1 (mL);
the temperature of the reaction is 30-90 ℃, and the time of the reaction is 0.5-10h.
9. Use of the microsphere according to any one of claims 1-4 as a transition metal Pd catalyst, in a coupling reaction catalyzed by a Pd catalyst, in a reduction reaction catalyzed by a Pd catalyst.
10. Use according to claim 9, wherein aniline, N-alkylaniline and/or N, N-dialkylaniline are prepared by catalytic reductive alkylation of nitrobenzene as catalyst for the Suzuki reaction, catalyzing the reduction of azide compounds to primary amines.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311029566.2A CN116747878B (en) | 2023-08-16 | 2023-08-16 | Magnetic nano microsphere and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311029566.2A CN116747878B (en) | 2023-08-16 | 2023-08-16 | Magnetic nano microsphere and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116747878A CN116747878A (en) | 2023-09-15 |
CN116747878B true CN116747878B (en) | 2023-12-05 |
Family
ID=87955480
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311029566.2A Active CN116747878B (en) | 2023-08-16 | 2023-08-16 | Magnetic nano microsphere and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116747878B (en) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100768632B1 (en) * | 2006-10-30 | 2007-10-18 | 삼성전자주식회사 | Method for dispersing nanoparticles and method for producing nanoparticles thin film using the same |
CN101184711A (en) * | 2005-05-27 | 2008-05-21 | 普罗梅鲁斯有限责任公司 | Nucleophilic heterocyclic carbene derivatives of pd(acac)2 for cross-coupling reactions |
CN102614896A (en) * | 2012-03-08 | 2012-08-01 | 昆明理工大学 | Preparation method of surface modified nano palladium/iron catalytic reducing agent |
CN104667945A (en) * | 2015-01-10 | 2015-06-03 | 安徽大学 | Supported palladium catalyst Fe3O4/SiO2Preparation of Pd and application in Suzuki reaction |
CN104971738A (en) * | 2015-07-07 | 2015-10-14 | 淮阴工学院 | Preparation method of magnetic nano palladium catalyst |
CN107824198A (en) * | 2017-11-09 | 2018-03-23 | 武汉工程大学 | A kind of preparation method and applications of the magnetic nano-catalyst of supported nano-gold |
CN108212211A (en) * | 2017-12-30 | 2018-06-29 | 武汉工程大学 | A kind of preparation method of the magnetic nano-catalyst of supported nano-gold |
CN115155614A (en) * | 2022-08-09 | 2022-10-11 | 国泰新科工业科技(宜兴)有限公司 | Preparation method and application of flower-shaped magnetic nano gold catalyst |
-
2023
- 2023-08-16 CN CN202311029566.2A patent/CN116747878B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101184711A (en) * | 2005-05-27 | 2008-05-21 | 普罗梅鲁斯有限责任公司 | Nucleophilic heterocyclic carbene derivatives of pd(acac)2 for cross-coupling reactions |
KR100768632B1 (en) * | 2006-10-30 | 2007-10-18 | 삼성전자주식회사 | Method for dispersing nanoparticles and method for producing nanoparticles thin film using the same |
CN102614896A (en) * | 2012-03-08 | 2012-08-01 | 昆明理工大学 | Preparation method of surface modified nano palladium/iron catalytic reducing agent |
CN104667945A (en) * | 2015-01-10 | 2015-06-03 | 安徽大学 | Supported palladium catalyst Fe3O4/SiO2Preparation of Pd and application in Suzuki reaction |
CN104971738A (en) * | 2015-07-07 | 2015-10-14 | 淮阴工学院 | Preparation method of magnetic nano palladium catalyst |
CN107824198A (en) * | 2017-11-09 | 2018-03-23 | 武汉工程大学 | A kind of preparation method and applications of the magnetic nano-catalyst of supported nano-gold |
CN108212211A (en) * | 2017-12-30 | 2018-06-29 | 武汉工程大学 | A kind of preparation method of the magnetic nano-catalyst of supported nano-gold |
CN115155614A (en) * | 2022-08-09 | 2022-10-11 | 国泰新科工业科技(宜兴)有限公司 | Preparation method and application of flower-shaped magnetic nano gold catalyst |
Also Published As
Publication number | Publication date |
---|---|
CN116747878A (en) | 2023-09-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108097316B (en) | Preparation method of MOFs nano material loaded with nano metal particles | |
CN111841610B (en) | Electron-rich single-atom Pt alloy intermetallic compound catalyst and preparation method thereof | |
CN109876801B (en) | Nano carbon supported high-dispersion platinum catalyst, preparation method thereof and application thereof in hydrogenation reaction of aromatic nitro compound | |
CN109679047B (en) | Preparation method of spherical covalent organic nano luminescent material | |
CN109317149A (en) | A kind of SiO of nickel-loaded2The preparation method and application of@C core-shell material | |
CN108855095B (en) | Methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO2Preparation method of (1) | |
CN110813281B (en) | Application of nano-carbon supported cluster-state palladium-based catalyst in preparation of primary amine by catalytic hydrogenation of nitrile compound | |
CN105618095B (en) | Porous nano carborundum load platinum catalyst and preparation and the application in alpha, beta-unsaturated aldehyde selective hydrogenation reaction | |
CN102641736A (en) | Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof | |
CN101049562A (en) | Catalyst for preparing halogeno anilin through catalytic hydrogenation of halogeno nitrobenzene and preparation method | |
CN113061091B (en) | Preparation method of N-alkylated derivative of primary amine compound | |
CN113019393B (en) | Platinum nano catalyst, preparation method thereof and method for synthesizing aromatic amine by selective hydrogenation of aromatic nitro compound | |
CN115646501B (en) | Cobalt monoatomic catalyst synthesized by molten salt method and application thereof | |
CN116747878B (en) | Magnetic nano microsphere and preparation method and application thereof | |
CN115007155B (en) | Supported nickel-containing catalyst, preparation method thereof and method for preparing olefin by catalyzing alkyne hydrogenation by using supported nickel-containing catalyst | |
CN110975924B (en) | Catalyst for preparing cyclohexanone by catalytic oxidation of cyclohexene, preparation method and application thereof | |
CN109912374B (en) | Method for preparing cis-pinane by hydrogenating alpha-pinene | |
CN110935481B (en) | Catalyst for selective hydrogenolysis of aromatic ether bond, preparation and application thereof | |
CN115155662B (en) | Method for preparing aromatic amine compound by hydrogenation of aromatic nitro compound and preparation method of palladium catalyst thereof | |
CN107721928A (en) | A kind of iron-based cyano-containing anion imidazole ion liquid and its preparation method and application | |
JPH0838901A (en) | Copper oxide/zirconium oxide catalyst and its preparation | |
CN1089038C (en) | Coated catalytic compositions including nickel, cobalt and molybdenum, and use thereof for preparing unsaturated aldehydes | |
CN109248682B (en) | Catalyst for oxalate hydrogenation and preparation method thereof | |
CN110180587A (en) | The preparation method and applications of functionalized silicon nanometer sheet loaded palladium catalyst | |
CN112023963B (en) | Catalyst for synthesizing 1, 4-butynediol and application |
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 |