CN106964403B - 一种磁性苯基膦钯复合催化剂及其应用 - Google Patents
一种磁性苯基膦钯复合催化剂及其应用 Download PDFInfo
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- boric acid
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- composite catalyst
- phosphine palladium
- phenyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- -1 halogenated aryl hydrocarbon Chemical class 0.000 claims abstract description 31
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 39
- 229910052681 coesite Inorganic materials 0.000 claims description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052682 stishovite Inorganic materials 0.000 claims description 17
- 229910052905 tridymite Inorganic materials 0.000 claims description 17
- ANZHFNXLFAJEOL-UHFFFAOYSA-N B(O)(O)OC(C)(C)C(C)(C)O.C1=CC=CC=C1 Chemical class B(O)(O)OC(C)(C)C(C)(C)O.C1=CC=CC=C1 ANZHFNXLFAJEOL-UHFFFAOYSA-N 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 11
- 239000002077 nanosphere Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043276 diisopropanolamine Drugs 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 3
- RSSDWSPWORHGIE-UHFFFAOYSA-N $l^{1}-phosphanylbenzene Chemical compound [P]C1=CC=CC=C1 RSSDWSPWORHGIE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims 3
- 239000012071 phase Substances 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 7
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000000725 suspension Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000908 ammonium hydroxide Substances 0.000 description 8
- 235000010338 boric acid Nutrition 0.000 description 8
- 229960002645 boric acid Drugs 0.000 description 8
- 229960004756 ethanol Drugs 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- JXMZUNPWVXQADG-UHFFFAOYSA-N 1-iodo-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1I JXMZUNPWVXQADG-UHFFFAOYSA-N 0.000 description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CYMXTKNOROVINH-UHFFFAOYSA-N OC(C)(C)C(C)(C)O.C1(=CC=CC=C1)OB(O)O Chemical compound OC(C)(C)C(C)(C)O.C1(=CC=CC=C1)OB(O)O CYMXTKNOROVINH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical compound ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 description 1
- AFMPMSCZPVNPEM-UHFFFAOYSA-N 2-bromobenzonitrile Chemical compound BrC1=CC=CC=C1C#N AFMPMSCZPVNPEM-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 1
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical group OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- CJNZAXGUTKBIHP-UHFFFAOYSA-N 2-iodobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1I CJNZAXGUTKBIHP-UHFFFAOYSA-N 0.000 description 1
- JDDAFHUEOVUDFJ-UHFFFAOYSA-N 2-iodobenzonitrile Chemical compound IC1=CC=CC=C1C#N JDDAFHUEOVUDFJ-UHFFFAOYSA-N 0.000 description 1
- KQDJTBPASNJQFQ-UHFFFAOYSA-N 2-iodophenol Chemical compound OC1=CC=CC=C1I KQDJTBPASNJQFQ-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ADOAGZYJBAATLP-UHFFFAOYSA-N COC(C1=CC=CC=C1)=O.[Br] Chemical compound COC(C1=CC=CC=C1)=O.[Br] ADOAGZYJBAATLP-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- LXDRHVXMGDKBEK-UHFFFAOYSA-N [B].C1=CC=CC=C1 Chemical class [B].C1=CC=CC=C1 LXDRHVXMGDKBEK-UHFFFAOYSA-N 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 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
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DYUWQWMXZHDZOR-UHFFFAOYSA-N methyl 4-iodobenzoate Chemical class COC(=O)C1=CC=C(I)C=C1 DYUWQWMXZHDZOR-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种磁性苯基膦钯复合催化剂及其应用,采用“一锅法”将卤代芳烃、联硼酸频那醇酯、醋酸盐、相转移催化剂和磁性苯基膦钯复合催化剂加入至1,4‑二氧六环溶剂体系中,在80‑110℃下搅拌,反应液过滤、洗涤、蒸馏获得固体,在溶剂中加入适量胺基乙二醇反应,然后水解,过滤洗涤,即得到取代苯硼酸。此方法反应条件温和,可适应多种卤代芳烃,可操作性强,磁性苯基膦钯复合催化剂用量少,可回收,连续使用5次,仍可得到较好转化,所得的取代的苯硼酸可广泛应用于化工、医药、生物和材料等领域。
Description
技术领域
本发明涉及材料科学中的贵金属催化剂技术领域以及药物化学和合成化学领域,特别是涉及一种磁性苯基膦钯复合催化剂及其应用。
背景技术
取代硼酸在化工医药、生物和材料等领域有很广泛的应用,目前这些领域对于取代苯硼酸的需求与日俱增。但是,传统的合成方法,有:锂试剂法、格氏试剂法。文献J. Org.Chem.,62(15),4943-4948,1997; Journal of Organometallic Chemistry 598(1),127-135, 2000; J. Org. Chem., 70(7): 2445-2454, 2005; Journal of ChemicalResearch, 38(12), 719-721; 2014 .对带有活性基团取代的芳烃耐受性差,反应均要求在极低温度下进行,因而活性基团取代苯硼酸的制备方法多数仍停留在实验阶段,难以实现工业化生产。
催化硼化法在极大程度解决了活性基团取代芳卤在金属试剂中耐受性差的问题。文献J. Org. Chem., 60(23), 7508-7510,1995;Applied Organometallic Chemistry,25(7), 537-541,2011; Synlett, 25(11), 1577-1584,2014; CN104785301A;CN104667945A; CN104971738A给出了各种催化剂的制备及应用,对各种活性基团有较好的适应能力,可以高效催化芳卤与频哪醇酯的偶联以及Suzuki反应。
这种方法可以用来制备各种活性基团取代的苯硼酸化合物,但是钯催化剂价格昂贵,提高催化剂的催化效率以及提高催化剂的回收率便是解决这一问题的关键。
发明内容
本发明主要解决的技术问题是提供一种磁性苯基膦钯复合催化剂及其应用,解决了活性基团取代苯硼酸用传统方法较难实现规模化生产的技术难题,采用磁性苯基膦钯复合催化剂进行的反应条件温和,可适应多种卤代芳烃,可操作性强,磁性苯基膦钯复合催化剂用量少,可回收,连续使用5次,仍可得到较好转化,所得的取代的苯硼酸可广泛应用于化工、医药、生物和材料等领域。
为解决上述技术问题,本发明采用的一个技术方案是:提供一种磁性苯基膦钯复合催化剂,所述磁性苯基膦钯复合催化剂是以超顺磁性Fe3O4@SiO2纳米微球作为载体,所述Fe3O4@SiO2纳米微球表面共价修饰苯基磷钯(Ⅱ),所述磁性苯基膦钯复合催化剂的结构式为:
。
提供一种磁性苯基膦钯复合催化剂的制备方法,包括步骤为:
(1)以氯化亚铁和三氯化铁为原料,先加入氨水再加入柠檬酸钠后,外磁场分离,得到Fe3O4颗粒,再分散到乙醇中得到Fe3O4悬浮液;
(2)Fe3O4悬浮液分散于乙醇、水和氨水的溶液中,加入四乙氧基硅脂,利用外加磁场分离,得到Fe3O4@SiO2纳米微球;
(3)Fe3O4悬浮液分散于乙醇中,加入氨水、磷配体(EtO)3Si(CH2)3PPh2得到Fe3O4@SiO2@(EtO)3Si(CH2)3PPh2;
(4)Fe3O4@SiO2@(EtO)3Si(CH2)3PPh2中加入氯化钯或醋酸钯、乙醇,外加磁场分离,得到磁性苯基膦钯复合催化剂。
在本发明一个较佳实施例中,所述磁性苯基膦钯复合催化剂的制备方法包括的具体步骤为:
(1)惰性气体保护下,将氯化亚铁、三氯化铁和去离子水混合加热至40℃,滴加氨水,搅拌30min后升温至80-120℃,加入柠檬酸钠水溶液搅拌数小时,停止反应,外加磁场分离,得到直径40-250nm的黑色Fe3O4颗粒,然后将所得黑色固体分散到一定体积乙醇溶液中制备成0.1 g mL-1的Fe3O4悬浮液;
(2)惰性气体保护下,取10 mL浓度为0.1g mL-1 Fe3O4乙醇悬浮液,加入总体积为60~120 mL的乙醇和水作为溶剂、1~5 mL氨水,分散均匀,加入1~10mL四乙氧基硅脂,室温搅拌1~12h,利用外加磁场分离,得到直径大小为80~350nm的Fe3O4@SiO2纳米微球;
(3)惰性气体保护下,向5 mL 0.1g mL-1 Fe3O4@SiO2乙醇悬浮液中加入无水乙醇120 mL,分散均匀,依次加入1~5 mL氨水、0.17~3.4g磷配体(EtO)3Si(CH2)3PPh2 ,反应24小时后得到修饰后的磁性配体Fe3O4@SiO2@(EtO)3Si(CH2)3PPh2;
(4)向0.1~1 g Fe3O4@SiO2@(EtO)3Si(CH2)3PPh2中依次加入5-50 mg氯化钯或醋酸钯、乙醇,室温反应4h,外加磁场分离,得到磁性苯基膦钯复合催化剂。
提供一种磁性苯基膦钯复合催化剂在制备取代苯硼酸中的应用。
在本发明一个较佳实施例中,所述磁性苯基膦钯复合催化剂在制备取代苯硼酸中的用量为0.01%~0.1%。
在本发明一个较佳实施例中,所述取代苯硼酸包含活性基团取代的芳基硼酸和活性基团取代的芳基硼酸频哪醇酯,结构式为:
。
提供一种取代苯硼酸的制备方法,包括步骤为:
(1)将卤代芳烃、联硼酸频那醇酯、碱、相转移催化剂、磁性苯基膦钯复合催化剂加入至1,4-二氧六环溶剂中得到取代苯硼酸频哪醇酯的反应液;
(2)对所述取代苯硼酸频哪醇酯的反应液后处理得到取代苯硼酸频哪醇酯;
(3)所述取代苯硼酸频哪醇酯与胺基乙二醇混合得到中间体铵盐;
(4)所述中间体铵盐用稀盐酸处理得到取代苯硼酸。
在本发明一个较佳实施例中,所述取代苯硼酸的制备方法包括的具体步骤为:
(1)惰性气体保护下,将卤代芳烃、联硼酸频那醇酯、碱、相转移催化剂、磁性苯基膦钯复合催化剂加入至1,4-二氧六环溶剂中,升温至 70-110℃,搅拌3-8h后得到取代苯硼酸频哪醇酯的反应液;
(2)将(1)得到的反应液过滤,有机相蒸干后用有机溶剂溶解,加水洗涤2-3次,蒸干有机相,得到取代苯硼酸频哪醇酯;
(3)向(2)得到的取代苯硼酸频哪醇酯,加入一定量溶剂,室温下滴加胺基乙二醇,维持搅拌0.5-5h,得到中间体铵盐;
(4)将(3)得到的中间体铵盐0-50℃下溶解于0.05-2 molL-1稀盐酸中,搅拌0.5-5h,过滤洗涤得到取代苯硼酸。
在本发明一个较佳实施例中,所述取代苯硼酸包含活性基团取代的芳基硼酸和活性基团取代的芳基硼酸频哪醇酯,结构式为:
;
步骤(1)中所述相转移催化剂为R4NX,其中R为H、C1-C18中一种或多种,X为Cl,Br,I中一种或多种;步骤(1)中所用的碱为MOAc,其中M为Li、Na、K、Cs中一种或多种;步骤(1)中所述卤代烃与联硼酸频那醇酯、碱、相转移催化剂、1,4-二氧六环的摩尔量比依次为1:1~1.5、1:2~4、1:0.05~0.5、1:10~25。
在本发明一个较佳实施例中,步骤(3)中所述溶剂为R1-O-R2或CnH2n+2,其中R1、R2为C1-C8中一种或多种,n=5,6,7,8;步骤(3)中所述胺基乙二醇为二乙醇胺、二异丙醇胺或二者混合物,所述卤代烃与胺的摩尔量比为1:1~5。
本发明的有益效果是:本发明的磁性苯基膦钯复合催化剂及其应用,在较为温和的条件下制备活性基团取代芳基硼酸;催化剂用量少,而且磁性钯复合催化剂在外加磁场作用下可以与反应介质快速分离,催化剂回收率大大提高,很大程度上降低了生产成本;磁性纳米微球的超大比表面积带来高负载率,该磁性钯复合催化剂应用于活性基团取代芳基硼酸的制备以及Suzuki偶联反应中,对各种活性基团取代的卤代烃均有较好的催化效果,均能达到接近等量的转化,催化剂连续使用5次,催化活性没有明显下降;将苯硼酸频哪醇酯与胺形成中间体铵盐,经水解得到硼酸的方法,解决了苯硼酸频哪醇酯在酸性条件下水解不彻底的问题,极大的提高了苯基硼酸的产率。
附图说明
为了更清楚地说明本发明实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其它的附图,其中:
图1是本发明的磁性二苯基膦钯复合催化剂中磁性核的电镜结构图,图中a和b为纳米Fe3O4粒子的TEM表征图,c和d为Fe3O4@SiO2纳米微球的TEM表征图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例一:
提供一种磁性苯基膦钯复合催化剂,所述磁性苯基膦钯复合催化剂是以超顺磁性Fe3O4@SiO2纳米微球作为载体,Fe3O4@SiO2纳米微球表面共价修饰二苯基磷钯(Ⅱ),所述磁性苯基膦钯复合催化剂的结构式为:
。
上述磁性苯基膦钯复合催化剂的制备过程如下:
(1) 氮气保护下,依次向250mL四口烧瓶中加入2.00g四水合氯化亚铁、2.44g三氯化铁、80mL去离子水。加热至40 ℃,滴加氨水9mL,搅拌30min后升温至85℃,加入47g质量浓度15%的柠檬酸钠水溶液搅拌2h,停止反应。待温度降至室温,外加磁场分离,得到黑色固体,用去离子水洗涤2次。向黑色固体中加入乙醇15mL,得到 Fe3O4悬浮液;
(2)氮气保护下,向Fe3O4乙醇悬浮液中,加入65mL乙醇、15mL去离子水和4 mL氨水,在超声仪中超声30min,加入5mL四乙氧基硅脂,室温搅拌4h。外加磁场分离,得到黑色固体,用去离子水洗涤2次,乙醇洗涤2次。将洗涤后固体加入无水乙醇制成0.1 g mL-1 Fe3O4@SiO2悬浮液。
(3)氮气保护下,取5mL 0.1 g mL-1 Fe3O4@SiO2悬浮液,加入乙醇30mL,在超声仪中超声30min,加入1mL氨水、0.52g磷配体(EtO)3Si(CH2)3PPh2 ,反应24小时后得到磁性配体0.53g Fe3O4@SiO2@(EtO)3Si(CH2)3PPh2;
(4)向0.53 g Fe3O4@SiO2@(EtO)3Si(CH2)3PPh2中依次加入8.86mg氯化钯,新蒸THF20mL,在超声仪中超声30min,室温反应4h,外加磁场分离,用新蒸THF洗涤3次,50℃干燥3小时,得到磁性苯基膦钯复合催化剂0.538g。
实施例二:
本实施方式与具体实施例一不同的是:步骤(2)中加入四乙氧基硅脂的量为1~10mL。其它步骤和实施方式与具体实施例一相同。
实施例三:
本实施方式与具体实施例一和二不同的是:步骤(4)中加入的是醋酸钯。其它步骤和实施方式与具体实施例一和二相同。
实施例四:
本实施案例磁性苯基膦钯复合催化剂在制备活性基团取代芳基硼酸中的应用,所述取代苯硼酸的具体制备步骤为:
(1)氮气保护下,向100mL四口烧瓶中加入2-硝基溴苯(2.03g,0.01mol)、双联硼频哪醇酯(3.31g,0.013mol)、醋酸钾(2.94g,0.030mol)、TBAB(0.32g,0.001mol)、磁性苯基膦钯复合催化剂(以钯含量计0.05%mol,0.0046g)、1,4-二氧六环50mL,磁力搅拌,加热至内温104℃,反应4h完全。
(2)待降至室温,外加磁场,回收磁性苯基膦钯复合催化剂,反应液减压抽滤,有机相选干,得到粘稠状液体,加入30mL CH2Cl2溶解,10mL饱和食盐水洗涤2次,CH2Cl2相选干,得到活性基团取代芳基频哪醇酯。
(3)将步骤(2)的产品加入至100mL四口烧瓶中,加入正己烷4mL,室温下,加入二乙醇胺3g,反应3h,得到中间体铵盐。
(4)将步骤(3)得到的白色固体铵盐加入至50mL圆底烧瓶,加入10mL 1M HCl,磁力搅拌下,40℃水解1h,待冷却至室温,减压抽滤,得到产品1.55g,收率93%。
实施例五:
本实施方式与具体实施例四不同的是:步骤(3)中加入的是二异丙醇胺,收率92.8%,其他与具体实施例四相同。
实施例六:
本实施方式与具体实施例四和五不同的是:磁性苯基膦钯复合催化剂应用于活性基团取代芳基硼酸的制备,所用的卤代芳烃为邻硝基溴苯、对硝基溴苯、对氰基溴苯、对溴苯甲酸甲酯、对羧基溴苯、对羟基溴苯、邻硝基氯苯、对硝基氯苯、对氰基氯苯、对氯溴苯、对羧基氯苯、邻羟基氯苯、邻碘硝基苯、对碘硝基苯、对羟基碘苯、对羧基碘苯、对氰基碘苯或对碘苯甲酸甲酯,其他与具体实施案例相同。本实施案例中的反应方程式如下:
反应情况如下:
实施例七:
本实施方式与具体实施例四至六不同的是:催化剂循环套用5次,其他与具体实施例四相同,下表为催化剂循环套用5次。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其它相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (3)
1.一种取代苯硼酸的制备方法,其特征在于,所述取代苯硼酸的制备方法包括步骤为:
(1)将卤代芳烃、联硼酸频哪醇酯、碱、相转移催化剂、磁性苯基膦钯复合催化剂加入至1,4-二氧六环溶剂中得到取代苯硼酸频哪醇酯的反应液,
其中所述磁性苯基膦钯复合催化剂是以超顺磁性Fe3O4@SiO2纳米微球作为载体,所述Fe3O4@SiO2纳米微球表面共价修饰苯基磷钯(Ⅱ),所述磁性苯基膦钯复合催化剂的结构式为:
,
所述取代苯硼酸包含活性基团取代的芳基硼酸和活性基团取代的芳基硼酸频哪醇酯,结构式为:
,
所述相转移催化剂为R4NX,其中R为H、C1-C18中一种或多种,X为Cl,Br,I中一种或多种,碱为MOAc,其中M为Li、Na、K、Cs中一种或多种,所述卤代芳烃与联硼酸频哪醇酯、碱、相转移催化剂、1,4-二氧六环的摩尔量比依次为1:1~1.5、1:2~4、1:0.05~0.5、1:10~25;
(2)对所述取代苯硼酸频哪醇酯的反应液后处理得到取代苯硼酸频哪醇酯;
(3)所述取代苯硼酸频哪醇酯与胺基乙二醇混合得到中间体铵盐;
(4)所述中间体铵盐用稀盐酸处理得到取代苯硼酸。
2.根据权利要求1所述的取代苯硼酸的制备方法,其特征在于,所述取代苯硼酸的制备方法包括的具体步骤为:
(1)惰性气体保护下,将卤代芳烃、联硼酸频哪醇酯、碱、相转移催化剂、磁性苯基膦钯复合催化剂加入至1,4-二氧六环溶剂中,升温至 70-110℃,搅拌3-8h后得到取代苯硼酸频哪醇酯的反应液;
(2)将(1)得到的反应液过滤,有机相蒸干后用有机溶剂溶解,加水洗涤2-3次,蒸干有机相,得到取代苯硼酸频哪醇酯;
(3)向(2)得到的取代苯硼酸频哪醇酯,加入一定量溶剂,室温下滴加胺基乙二醇,维持搅拌0.5-5h,得到中间体铵盐;
(4)将(3)得到的中间体铵盐0-50℃下溶解于0.05-2 molL-1稀盐酸中,搅拌0.5-5h,过滤洗涤得到取代苯硼酸。
3.根据权利要求1所述的取代苯硼酸的制备方法,其特征在于,步骤(3)中所述溶剂为R1-O-R2或CnH2n+2,其中R1、R2为C1-C8中一种或多种,n=5,6,7,8;步骤(3)中所述胺基乙二醇为二乙醇胺、二异丙醇胺或二者混合物,所述卤代芳烃与胺的摩尔量比为1:1~5。
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