CN111974457A - Catalyst for synthesizing substituted ketone compound and preparation method thereof - Google Patents
Catalyst for synthesizing substituted ketone compound and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- -1 ketone compound Chemical class 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 17
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 17
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 5
- 150000002576 ketones Chemical class 0.000 claims abstract description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 74
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 13
- 239000012043 crude product Substances 0.000 claims description 11
- 150000008062 acetophenones Chemical class 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- UKVQBONVSSLJBB-UHFFFAOYSA-N 2-pyridin-2-ylacetonitrile Chemical compound N#CCC1=CC=CC=N1 UKVQBONVSSLJBB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- IRAARPXLWJLRDS-UHFFFAOYSA-N CC(C)=CC(CS(NO)(=O)=O)=O Chemical compound CC(C)=CC(CS(NO)(=O)=O)=O IRAARPXLWJLRDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 4
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- KUXDQQMEFBFTGX-UHFFFAOYSA-N [N].P Chemical compound [N].P KUXDQQMEFBFTGX-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 2
- QGGZBXOADPVUPN-UHFFFAOYSA-N beta-phenylpropiophenone Natural products C=1C=CC=CC=1C(=O)CCC1=CC=CC=C1 QGGZBXOADPVUPN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- GQCYRRORMLYXON-UHFFFAOYSA-N 1-(2-bromophenyl)-3-phenylpropan-1-one Chemical compound BrC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 GQCYRRORMLYXON-UHFFFAOYSA-N 0.000 description 1
- GQNOPFDKLUGQEC-UHFFFAOYSA-N 1-(4-chlorophenyl)-3-phenylpropan-1-one Chemical compound C1=CC(Cl)=CC=C1C(=O)CCC1=CC=CC=C1 GQNOPFDKLUGQEC-UHFFFAOYSA-N 0.000 description 1
- WMPHLIJZKDSFFR-UHFFFAOYSA-N 1-(4-methoxyphenyl)-3-phenylpropan-1-one Chemical compound C1=CC(OC)=CC=C1C(=O)CCC1=CC=CC=C1 WMPHLIJZKDSFFR-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- MMNLHUHQFDVPSQ-UHFFFAOYSA-N N=C=O.CCO[Si](OCC)(OCC)C(C)C Chemical compound N=C=O.CCO[Si](OCC)(OCC)C(C)C MMNLHUHQFDVPSQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
- C07F15/004—Iridium compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for synthesizing substituted ketone compounds and a preparation method thereof, belonging to the field of chemical materials and medicines. The invention obtains the nitrogen-phosphorus-containing ligand through organic synthesis, and the ligand is combined with iridium chloride and then loaded on an MCM-41 carrier to prepare the MCM-41-loaded nitrogen-phosphorus-containing ligand-containing iridium catalyst. The catalyst prepared by the method can be used for catalytically synthesizing substituted ketone compounds and bisphenol F. The novel iridium heterogeneous catalyst containing the nitrogen-containing phosphine ligand is an environment-friendly catalyst, has the advantages of high catalytic efficiency, mild reaction conditions, reusability of the catalyst and the like compared with the conventional experimental scheme for synthesizing ketone reaction, and accords with the development concept of environmental protection and atom economy; when the catalyst is used for bisphenol F synthesis reaction, the catalytic activity is stronger, the application range is wide, and the catalyst has good application prospect.
Description
Technical Field
The invention relates to a catalyst for synthesizing substituted ketone compounds and a preparation method thereof, belonging to the field of chemical materials and medicines.
Background
Because of the special structure of the substituted ketone compounds, many substituted ketone compounds are important intermediates in organic synthesis. Because of its bright prospect in organic synthesis, it has received much attention and research interest from domestic and foreign scientists in recent years. In recent years, with the improvement of environmental awareness of people, the focus of people is on finding a catalyst which is green, environment-friendly, efficient and environment-friendly, and can be recycled for synthesizing substituted ketone compounds.
Transition metals have been widely concerned in catalytic reactions in recent years, and iridium has the advantages of abundant sources, strong stability of the generated metal complex, and the like, and has relatively active chemical properties, so that iridium has wide application in the field of metal catalysis. The prior art does not disclose a recoverable pyrazoline iridium phosphate-containing catalyst for synthesizing substituted ketone compounds.
Disclosure of Invention
Aiming at the defects of the traditional method for synthesizing substituted ketone compounds, the invention provides a heterogeneous catalyst with stronger catalytic performance, which is prepared by using MCM-41 as a carrier and loading an iridium complex containing a nitrogen-containing phosphine ligand. The catalyst is used in the reaction of synthesizing substituted ketone compounds, has good catalytic effect, and is found to be reusable for 5 times without obvious reduction of catalytic activity by carrying out a recycling experiment on the catalyst. Meanwhile, the catalyst can also be used in the synthesis of bisphenol F.
First, the first object of the present invention is to provide a method for preparing a catalyst for synthesizing substituted ketones, the method comprises the following steps:
in an embodiment of the present invention, the method specifically includes the steps of:
(1) at 0-10 deg.C, CF3Mixing COOH and (isopropylidene acetone sulfonyl) hydroxylamine, reacting for 1-2h, adding ice water into the mixture after the reaction is finished, carrying out solid-liquid separation, taking a solid phase, and washing to be neutral to obtain a product 1 a;
(2) dissolving 2-pyridine acetonitrile in dichloromethane, dropwise adding dichloromethane solution of the product 1a prepared in the step (1), reacting at 20-40 ℃ for 1-2h, performing solid-liquid separation to obtain a solid phase, washing to obtain a white solid, adding methanol into the white solid at 0-10 ℃, stirring, and adding K while stirring2CO3Stirring for 1-1.5h to obtain a crude product, adding water into the crude product, extracting with dichloromethane, collecting an organic phase, and purifying to obtain a red solid 1 b;
(3) at the temperature of 0-15 ℃, the molar ratio of 1:1, placing the red solid 1b and triethylamine in a reaction vessel, adding dichloromethane into the reaction vessel for dissolving, dropwise adding diphenyl phosphine chloride with the same mole as the red solid 1b, reacting at 20-40 ℃ for 12-16h, after the reaction is finished, carrying out solid-liquid separation to obtain a liquid phase, carrying out reduced pressure spin drying on the obtained liquid phase, and then recrystallizing with anhydrous ether and trichloromethane to obtain a product 1 c;
(4) reacting the product 1c prepared in the step (3) with isocyanatopropyltriethoxysilane in a molar ratio of 1: feeding materials into a reaction container according to the molar ratio of 1.6, adding dichloromethane for dissolution, and reacting for 12-16h at the temperature of 20-40 ℃; after the reaction is finished, performing reduced pressure spin drying on the reacted product, and purifying to obtain a product 1 d;
(5) putting the product 1d prepared in the step (4) and equimolar iridium chloride into a reaction vessel in the presence of nitrogen, adding ethylene glycol ethyl ether into the mixture, and stirring for 24-32h at 100-110 ℃; after the reaction is finished, centrifugally separating the reaction liquid, washing for a plurality of times, and finally drying to obtain a solid 1 e;
(6) and (2) under the condition of nitrogen, placing the solid 1e and MCM-41 which are prepared in the step (5) in equal mass ratio into a reaction vessel, then adding toluene, reacting for 24-36h at 110-120 ℃, centrifugally separating after the reaction is finished, washing for several times, and finally drying to obtain the solid, namely the MCM-41 supported nitrogen-containing phosphine ligand iridium catalyst.
In one embodiment of the invention, the molar ratio of the 2-pyridineacetonitrile to the product 1a in step (2) is 2 to 3: 4.
In an embodiment of the present invention, the method specifically includes:
(1) at 0 deg.C, using 10mL of CF31g of (isopropylidene acetone sulfonyl) hydroxylamine is deprotected by COOH and reacted for 1 h; after the reaction is finished, adding ice water into the mixture, performing suction filtration, collecting a filter cake, and washing the filter cake to be neutral for multiple times by using distilled water to obtain a product 1 a;
(2) dissolving 2-pyridine acetonitrile in dichloromethane, dropwise adding 1a dichloromethane solution into the dichloromethane, reacting for 1h at 20-40 ℃, filtering after the reaction is finished, collecting a filter cake, washing with dichloromethane, adding a methanol solution into the obtained white solid at 0 ℃, stirring vigorously, and adding K2CO3Stirring for 1h, adding distilled water into the obtained crude product, extracting with dichloromethane, collecting an organic phase, and finally purifying by using a column chromatography method to obtain a red solid 1 b;
(3) at 0 ℃, 1b and triethylamine Et are mixed in an equimolar ratio3N in a round-bottom flask, followed by addition of dichloromethane and dropwise addition of diphenylphosphine chloride in equimolar amount to the red solid 1b, at 0-40 deg.CReacting for 12-16h, after the reaction is finished, performing suction filtration, collecting filtrate, performing reduced pressure spin drying on the filtrate, and then recrystallizing with anhydrous ether and trichloromethane to obtain a pure product 1 c;
(4) reacting the product 1c with isopropyltriethoxysilane isocyanate in a molar ratio of 1: feeding materials into a round-bottom flask according to the molar ratio of 1.6, adding dry dichloromethane for dissolving, reacting at room temperature for 12 hours, after the reaction is finished, performing reduced pressure spin drying on a crude product, and performing column chromatography to obtain a pure product 1 d;
(5) putting 1d obtained in the step (4) and equimolar iridium chloride into a round-bottom flask in the presence of nitrogen, adding ethylene glycol ethyl ether into the round-bottom flask, and stirring the mixture for 24 hours at the temperature of 110 ℃; after the reaction is finished, centrifuging the reaction solution, washing for a plurality of times, and finally drying to obtain a solid 1 e;
(6) under the condition of nitrogen, placing the solid 1e and MCM-41 in equal mass ratio in a Schlenk bottle, then adding toluene to react for 24 hours at 110 ℃, centrifuging a reaction crude product after the reaction is finished, washing for a plurality of times, and finally drying to obtain the solid, namely the MCM-41 supported nitrogen-containing phosphine ligand iridium catalyst.
The second purpose of the invention is to provide the catalyst prepared by the method, namely the MCM-41 iridium catalyst loaded with the nitrogen-containing phosphine ligand.
The third purpose of the invention is to provide the application of the catalyst in the reaction of synthesizing substituted ketone compounds and bisphenol F.
The fourth purpose of the invention is to provide a method for catalyzing the alkylation reaction of acetophenone derivatives and benzyl alcohol, wherein the MCM-41 loaded nitrogen-containing phosphine ligand iridium catalyst prepared by the method is used as a catalyst.
In an embodiment of the present invention, the method specifically includes: feeding the acetophenone derivative and benzyl alcohol according to a molar ratio of 1.1:1, adding the mixture into a reactor with the molar ratio of the acetophenone derivative to the benzyl alcohol being 1: 20 of NaOH, 10-15% of MCM-41 loaded nitrogen-containing phosphine ligand iridium catalyst in molar weight of benzyl alcohol, and reacting for 10-16 h by taking toluene as a reaction solvent to obtain the substituted ketone compound.
In one embodiment of the present invention, the acetophenone derivative comprises acetophenone.
In one embodiment of the invention, experiments show that the catalyst has universal tolerance no matter whether the acetophenone derivative substrate is an electron-withdrawing group or an electron-donating group, and the reaction byproduct is only water, which is consistent with green chemistry development.
In one embodiment of the present invention, the catalyst can be recycled by: the previously used MCM-41 loaded iridium catalyst with nitrogen-containing phosphine ligand was centrifuged many times with water and methanol, washed, and dried, i.e., ready for the next cycle.
The fifth object of the present invention is to provide a method in the reaction for synthesizing bisphenol F, which uses the above catalyst as a reaction catalyst.
In one embodiment of the invention, the method comprises: heating phenol to 60-70 ℃ to be completely melted, then adding the catalyst and formaldehyde, reacting for 5-8 h at 40-60 ℃, adding sodium bicarbonate to reach the pH value of 5-6 after the reaction is finished, collecting an organic phase, distilling under reduced pressure, and adding concentrated hydrochloric acid into the residual product after the distillation is finished until a large amount of white precipitate is generated, namely a pure bisphenol F product, wherein the molar ratio of the phenol to the catalyst to the formaldehyde is 1: 0.2-0.3: 0.4-0.5.
The invention has the following beneficial effects:
(1) compared with the traditional method, the MCM-41 loaded metal iridium heterogeneous catalyst containing the nitrogen phosphine ligand has higher catalytic efficiency and catalytic performance, and compared with the traditional synthesis of substituted ketones, the reaction process of the invention does not use strong acid and toxic halogenated hydrocarbon, thereby being more environment-friendly and green. In addition, the catalyst can be recycled after being used, and experiments show that the catalytic activity is not obviously reduced after being recycled for 5 times, and a good catalytic effect can be still kept.
(2) The catalyst prepared by the invention can also be used for catalyzing the reaction for synthesizing bisphenol F, and has stronger catalytic activity and good catalytic effect. Therefore, the catalyst has wide application scene and good application prospect.
Drawings
FIG. 1 is an SEM photograph of the catalyst prepared in example 1.
Detailed Description
The calculation formula of the yield is as follows: yield-the actual mass of the target product obtained/theoretically 100% of the target product obtained.
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
In the following, the applicant has made some specific experiments on the present invention, and describes the synthesis steps of the MCM-41 supported iridium catalyst containing a nitrogen phosphine ligand, and the specific steps of using such catalyst to catalyze the alkylation reaction of benzyl alcohol and acetophenone derivatives to produce substituted ketone compounds, and the specific experimental methods of the catalyst recovery experiments. These are merely intended to be exhaustive of the invention and do not limit the scope of the invention in any way.
Example 1: synthesis of iridium catalysts containing nitrogen phosphine ligands
(1) Synthesis of 1 a: 1g N-Boc-O- (isopropylideneacetosulfonyl) hydroxylamine was placed in a 100mL round bottom flask at 0 deg.C and 10mL CF was added portionwise3COOH, and stirring for 1h at 0 ℃; after the reaction is finished, slowly adding ice water into the mixture, stirring for 15min again, performing suction filtration, collecting a filter cake, and washing the filter cake with distilled water for multiple times until the pH value is 7 to obtain a colorless solid which is the product 1 a;
(2) synthesis of 1 b: dissolving 8mmol of 2-pyridine acetonitrile in 20mL of dichloromethane, dissolving 12mmol of 1a in 30mL of dichloromethane, dropwise adding the 1a dichloromethane solution into the 2-pyridine acetonitrile dichloromethane solution, reacting at room temperature for 1h after the dropwise adding is finished, performing suction filtration after the reaction is finished, collecting a filter cake, and washing with dichloromethane for several times to obtain a white solid; the resulting white solid was placed in a 100mL round-bottom flask at 0 ℃ and added with a methanol solution and stirred vigorously while adding 8mmol K2CO3After being stirred vigorously for 1h, the mixture is stirred continuously for 1h at room temperature and then the reaction is stopped; diluting the obtained crude product with distilled water, extracting with dichloromethane for 2-3 times, collecting organic phaseRotating and evaporating the organic phase to dryness, and finally purifying by using a column chromatography to obtain a red solid 1 b;
(3) synthesis of 1 c: 5mmol of 1b, 5mmol Et at 0 deg.C3Placing N in a 50mL round-bottom flask, then adding 20mL dichloromethane, dropwise adding 5mmol diphenyl phosphine chloride, stirring at room temperature for 12h, after the reaction is finished, carrying out suction filtration, collecting filtrate, carrying out reduced pressure spin drying on the filtrate, and then recrystallizing with anhydrous ether and trichloromethane to obtain a pure product 1 c;
(4) synthesis of 1 d: placing 5mmol of 1c, 8mmol of isocyanatopropyl triethoxysilane in a 50mL round-bottom flask at room temperature, adding 10mL of dried dichloromethane, stirring at room temperature for 12h, after the reaction is finished, performing reduced pressure spin drying on the crude product, and performing column chromatography to obtain a pure product 1 d;
(5) synthesis of 1 e: in N2Under the condition, 5mmol of 1d, 5mmol of IrCl3Placing the mixture in a 50mL round-bottom flask, adding 10mL ethylene glycol ethyl ether into the flask, placing the flask in an oil bath kettle at 110 ℃ for magnetic stirring for 24 hours, after the reaction is finished, centrifuging the obtained suspension, washing the suspension for 3-4 times by using methanol and ethanol respectively, and finally placing the suspension in an oven at 60 ℃ for drying to obtain a solid 1 e;
(6) under the condition of nitrogen, 1g of solid 1e and 1g of MCM-41 are placed in a 100mL Schlenk bottle, then 30mL of toluene is added, the mixture is placed in a 110 ℃ oil bath kettle and stirred magnetically for 24 hours, after the reaction is cooled to room temperature, the reaction crude product is centrifuged, and is washed for a plurality of times by methanol and absolute ethyl alcohol, and finally the reaction crude product is placed in a 60 ℃ oven to be dried, so that the solid MCM-41 supported nitrogen-containing phosphine ligand iridium catalyst is obtained.
FIG. 1 is an SEM image of the catalyst prepared, from which it can be seen that an iridium catalyst containing a nitrogen-containing phosphine ligand has been successfully supported on MCM-41.
Example 2: synthesis of substituted ketone compound by catalyzing reaction of benzyl alcohol and acetophenone
Putting 1mmol of benzyl alcohol and 1.1mmol of acetophenone into a 25mL reaction bottle, adding 0.1mmol of the catalyst prepared in example 1 and 0.05mmol of NaOH, using toluene as a reaction solvent, placing the mixture in a 120 ℃ oil bath kettle, magnetically stirring for 12 hours, adding distilled water after the reaction is finished and cooled to room temperature, extracting for 3 times by using ethyl acetate, collecting an organic phase, rotating and evaporating the organic phase to dryness, and finally separating by using column chromatography to obtain a product 1, 3-diphenylpropane-1-one, wherein the reaction yield is 88% by chromatography.
Example 3: synthesis of substituted ketone compound by catalyzing reaction of benzyl alcohol and 4-methoxyacetophenone
Putting 1mmol of benzyl alcohol and 1.1mmol of 4-methoxyacetophenone into a 25mL reaction bottle, adding 0.1mmol of the catalyst prepared in example 1 and 0.05mmol of NaOH, using toluene as a reaction solvent, placing the mixture in a 120 ℃ oil bath kettle, magnetically stirring for 12 hours, adding distilled water after the reaction is finished and cooled to room temperature, extracting for 3 times by using ethyl acetate, collecting an organic phase, carrying out rotary evaporation to dryness, and finally separating by using column chromatography to obtain the product 1- (4-methoxyphenyl) -3-phenylpropan-1-one, wherein the reaction yield is 89% by chromatography.
Example 4: synthesis of substituted ketone compound by catalyzing reaction of benzyl alcohol and 4-methylacetophenone
Putting 1mmol of benzyl alcohol and 1.1mmol of 4-methylacetophenone into a 25mL reaction bottle, adding 0.1mmol of the catalyst prepared in example 1 and 0.05mmol of NaOH, using toluene as a reaction solvent, placing the mixture in a 120 ℃ oil bath, magnetically stirring for 12 hours, adding distilled water after the reaction is finished and cooled to room temperature, extracting for 3 times by using ethyl acetate, collecting an organic phase, carrying out rotary evaporation to dryness, and finally separating by using column chromatography to obtain a product of 3-phenyl-1- (p-tolyl) propane-1-ketone, wherein the reaction yield is 85 percent according to chromatographic analysis
Example 5: synthesis of substituted ketone compound by catalyzing reaction of benzyl alcohol and 4-chloroacetophenone
Putting 1mmol of benzyl alcohol and 1.1mmol of 4-chloroacetophenone into a 25mL reaction bottle, adding 0.1mmol of the catalyst prepared in example 1 and 0.05mmol of NaOH, using toluene as a reaction solvent, placing the mixture in a 120 ℃ oil bath, magnetically stirring for 12 hours, adding distilled water after the reaction is finished and cooled to room temperature, extracting for 3 times by using ethyl acetate, collecting an organic phase, carrying out rotary evaporation to dryness, and finally carrying out column chromatography separation to obtain the product 1- (4-chlorophenyl) -3-phenylpropan-1-one, wherein the reaction yield is 90% by chromatography.
Example 6: synthesis of substituted ketone compound by catalyzing reaction of benzyl alcohol and 2-bromoacetophenone
Putting 1mmol of benzyl alcohol and 1.1mmol of 2-bromoacetophenone into a 25mL reaction bottle, then adding 0.1mmol of the catalyst prepared in example 1 and 0.05mmol of NaOH, using toluene as a reaction solvent, placing the mixture in a 120 ℃ oil bath kettle, magnetically stirring for 12 hours, adding distilled water after the reaction is finished and cooled to room temperature, extracting for 3 times by using ethyl acetate, collecting an organic phase, carrying out rotary evaporation to dryness, and finally separating by using column chromatography to obtain the product 1- (2-bromophenyl) -3-phenylpropan-1-one, wherein the reaction yield is 89% by chromatography.
Example 7: repeated use experiment of solid catalyst
Putting 1mmol of benzyl alcohol and 1.1mmol of acetophenone into a 25mL reaction bottle, then adding 0.1mmol of the catalyst prepared in example 1 and 0.05mmol of NaOH, using toluene as a reaction solvent, placing the mixture in a 120 ℃ oil bath kettle, magnetically stirring for 12 hours, filtering out a solid catalyst after the reaction is finished and cooled to room temperature, washing the solid catalyst with ethanol and distilled water for a plurality of times, drying the solid catalyst at 80 ℃ for 3 hours, putting the recovered catalyst into the reaction again for recycling, and finally recycling the catalyst for 5 times, wherein the obtained results are shown in the following table 1.
TABLE 1 catalyst recycle reaction yield at different recycle times
Example 8: catalytic synthesis of bisphenol F
Heating 5mmol of phenol to 70 ℃ to be completely melted, then adding 1.5mmol of the catalyst, finally adding 2mmol of formaldehyde, reacting at 60 ℃ for 6h, adding sodium bicarbonate solid after the reaction is finished until the pH value is 6, collecting an organic phase, distilling under reduced pressure, and adding concentrated hydrochloric acid into the residual product after the distillation is finished until a large amount of white precipitate is generated, namely the bisphenol F product. Yield: 71 percent.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
2. the method according to claim 1, wherein the method comprises the following steps:
(1) at 0-10 deg.C, CF3Mixing COOH and (isopropylidene acetone sulfonyl) hydroxylamine, reacting for 1-2h, adding ice water into the mixture after the reaction is finished, carrying out solid-liquid separation, taking a solid phase, and washing to be neutral to obtain a product 1 a;
(2) dissolving 2-pyridine acetonitrile in dichloromethane, dropwise adding dichloromethane solution of the product 1a prepared in the step (1), reacting at 20-40 ℃ for 1-2h, performing solid-liquid separation to obtain a solid phase, washing to obtain a white solid, adding methanol into the white solid at 0-10 ℃, stirring, and adding K while stirring2CO3Stirring for 1-1.5h to obtain a crude product, adding water into the crude product, extracting with dichloromethane, collecting an organic phase, and purifying to obtain a red solid 1 b;
(3) at the temperature of 0-15 ℃, the molar ratio of 1:1, placing the red solid 1b and triethylamine in a reaction vessel, adding dichloromethane into the reaction vessel for dissolving, dropwise adding diphenyl phosphine chloride with the same mole as the red solid 1b, reacting at 20-40 ℃ for 12-16h, after the reaction is finished, carrying out solid-liquid separation to obtain a liquid phase, carrying out reduced pressure spin drying on the obtained liquid phase, and then recrystallizing with anhydrous ether and trichloromethane to obtain a product 1 c;
(4) reacting the product 1c prepared in the step (3) with isocyanatopropyltriethoxysilane in a molar ratio of 1: feeding materials into a reaction container according to the molar ratio of 1.6, adding dichloromethane for dissolution, and reacting for 12-16h at the temperature of 20-40 ℃; after the reaction is finished, performing reduced pressure spin drying on the reacted product, and purifying to obtain a product 1 d;
(5) putting the product 1d prepared in the step (4) and equimolar iridium chloride into a reaction vessel in the presence of nitrogen, adding ethylene glycol ethyl ether into the mixture, and stirring for 24-32h at 100-110 ℃; after the reaction is finished, centrifugally separating the reaction liquid, washing for a plurality of times, and finally drying to obtain a solid 1 e;
(6) and (2) under the condition of nitrogen, placing the solid 1e and MCM-41 which are prepared in the step (5) in equal mass ratio into a reaction vessel, then adding toluene, reacting for 24-36h at 110-120 ℃, centrifugally separating after the reaction is finished, washing for several times, and finally drying to obtain the solid, namely the MCM-41 supported nitrogen-containing phosphine ligand iridium catalyst.
3. The method for preparing the catalyst for synthesizing the substituted ketone compound according to claim 2, wherein the molar ratio of the 2-pyridineacetonitrile to the product 1a in the step (2) is 2-3: 4.
4. The catalyst prepared by the preparation method of the catalyst for synthesizing the substituted ketone compound according to any one of claims 1 to 3.
5. The use of the catalyst of claim 4 in reactions for the synthesis of substituted ketones, and for the synthesis of bisphenol F.
6. A process for catalyzing the alkylation of an acetophenone derivative with benzyl alcohol, which comprises using the catalyst of claim 4 as a catalyst.
7. The method of claim 6, wherein the method specifically comprises the following steps: feeding the acetophenone derivative and benzyl alcohol according to a molar ratio of 1.1:1, adding the mixture into a reactor with the molar ratio of the acetophenone derivative to the benzyl alcohol being 1: 20 NaOH and the catalyst of claim 4, and taking toluene as a reaction solvent, and reacting for 10-16 h to obtain the substituted ketone compound.
8. The method for catalyzing the alkylation reaction of the acetophenone derivative and the benzyl alcohol according to claim 7, wherein the amount of the catalyst is 10-15% of the molar amount of the benzyl alcohol.
9. A process for the synthesis of bisphenol F, characterized in that it comprises using as catalyst the catalyst according to claim 4.
10. The method of claim 9, wherein the method comprises: heating phenol to 60-70 ℃ to completely melt, then adding the catalyst and formaldehyde according to claim 4, reacting at 40-60 ℃ for 5-8 h, adding sodium bicarbonate to reach a pH value of 5-6 after the reaction is finished, collecting an organic phase, distilling under reduced pressure, and adding concentrated hydrochloric acid to the residual product after the distillation is finished until a large amount of white precipitate is generated, namely a pure bisphenol F product, wherein the molar ratio of the phenol to the catalyst to the formaldehyde is 1: 0.2-0.3: 0.4-0.5.
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