CN108993599A - A kind of functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine and preparation method thereof - Google Patents
A kind of functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 59
- 239000010703 silicon Substances 0.000 claims abstract description 59
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 34
- -1 iodo- 2,6- diisopropyl phenyl Chemical group 0.000 claims abstract description 33
- LRDJLICCIZGMSB-UHFFFAOYSA-N ethenyldiazene Chemical compound C=CN=N LRDJLICCIZGMSB-UHFFFAOYSA-N 0.000 claims abstract description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 12
- PWRBCZZQRRPXAB-UHFFFAOYSA-N 3-chloropyridine Chemical compound ClC1=CC=CN=C1 PWRBCZZQRRPXAB-UHFFFAOYSA-N 0.000 claims abstract description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 67
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- 230000035484 reaction time Effects 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 229960004756 ethanol Drugs 0.000 claims description 10
- NNYBQONXHNTVIJ-UHFFFAOYSA-N etodolac Chemical group C1COC(CC)(CC(O)=O)C2=C1C(C=CC=C1CC)=C1N2 NNYBQONXHNTVIJ-UHFFFAOYSA-N 0.000 claims description 10
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 10
- 229940063718 lodine Drugs 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 208000011580 syndromic disease Diseases 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 229940015043 glyoxal Drugs 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- ILVUABTVETXVMV-UHFFFAOYSA-N hydron;bromide;iodide Chemical compound Br.I ILVUABTVETXVMV-UHFFFAOYSA-N 0.000 claims description 4
- WCGIGOVLOFXAMG-UHFFFAOYSA-N silver;trifluoromethanesulfonic acid Chemical compound [Ag].OS(=O)(=O)C(F)(F)F WCGIGOVLOFXAMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 3
- GGRHYQCXXYLUTL-UHFFFAOYSA-N chloromethyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OCCl GGRHYQCXXYLUTL-UHFFFAOYSA-N 0.000 claims description 3
- 238000007306 functionalization reaction Methods 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims 1
- SRLROPAFMUDDRC-INIZCTEOSA-N ethyl N-benzoyl-L-tyrosinate Chemical group C([C@@H](C(=O)OCC)NC(=O)C=1C=CC=CC=1)C1=CC=C(O)C=C1 SRLROPAFMUDDRC-INIZCTEOSA-N 0.000 abstract 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 13
- 230000006872 improvement Effects 0.000 description 9
- 150000001500 aryl chlorides Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- LBYUOOWXKZFPSX-UHFFFAOYSA-N CC(C)C1=C(C(=CC=C1)C(C)C)NI Chemical compound CC(C)C1=C(C(=CC=C1)C(C)C)NI LBYUOOWXKZFPSX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 150000001499 aryl bromides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- ZYDSTVMBNBPPLQ-UHFFFAOYSA-N chloromethyl pentanoate Chemical compound CCCCC(=O)OCCl ZYDSTVMBNBPPLQ-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
Abstract
The present invention discloses a kind of functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine and the preparation method, it may be assumed that a, the preparation iodo- 2,6-DIPA of 4-；B, bis- (4-I-2,6- diisopropyl phenyl) diaza butadiene are prepared using a；C, bis- (the iodo- 2,6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- salt of 1,3- are prepared using b；D, catalyst is made with bis- (acetonitriles) (1,5- cyclo-octadiene) tetrafluoride rhodium, c reacts to obtain IPr function silicon source with triethoxysilane；E, the dilute hydrochloric acid liquid that BTEE skeleton silicon source is added to P123 and sodium chloride is reacted into copolymerization with IPr function silicon source；F, by reaction solution aging obtained by e；G, to remove obtained by f template it is dry NHC@PMO carrier；H, NHC@PMO carrier, palladium chloride and potassium carbonate are reacted into obtain Pd-NHC@PMO in 3- chloropyridine solution.
Description
Technical field
The present invention relates to catalyst preparation technologies, and in particular to a kind of order mesoporous nano-silicon of novel load palladium complex
Material.
Background technique
The functionalized silicon source of N- heterocycle carbine (IPr function silicon source): i.e. 1,3-bis (2,6-diisopropyl-4-
(triethoxysilyl) phenyl) -1H-imidazol-3-iumtrifluoromethanesulfonate, also referred to as 1,3- is bis-
(4- triethoxysilyl -2,6- diisopropyl phenyl) -1H- imidazoles -3- trifluoro-methanyl sulfonate is a kind of silicon source.Pd
The Suzuki-Miyaura coupling reaction of catalysis is the substantially anti-of synthesis multiclass polymer, agricultural chemicals and medical compounds
It answers.Due to aryl chloride as substrate use compared with aryl bromide and iodide, be easily obtained and at low cost, be one
The ideal coupled substrate of kind.However, the coupling activity of aryl chloride is lower for heterogeneous catalysis, it is challenging
's.The heterogeneous coupling report of the Suzuki-Miyaura coupling reaction of aryl chloride is seldom.Pd- phosphine system can be effectively
Promote the coupling of aryl chloride, but there is high toxicity and low stability in air.However, N- heterocycle carbine complex compound is such as
Pd-IPr [bis- (2,6- diisopropyl phenyl) imidazoles -2- subunits of IPr=N, N-] is not only in the Suzuki- of aryl chloride
There is comparable activity with Pd- phosphine complex compound in Miyaura coupling, and also stable in air, toxicity is low, meets greenization
Theory.
And pass through the triethoxysilane in IPr function silicon source and BTEE organosilan in one pot by template cocondensation
The order mesoporous organosilicon material (NHC@PMO) of synthesis.There are many unique advantages for this kind of material, such as due to drawing in carrier
The organic moiety entered is self assembly on a molecular scale, so that organic moiety is more equally distributed in the frame of material, without
It is to be grafted on the hole surface of material；Formed order mesoporous organosilicon material (NHC@PMO) surface area with higher, orderly
Nano pore and lesser diffusional resistance；N- heterocycle carbine complex compound is not only even in the Suzuki-Miyaura of aryl chloride
There is comparable activity, and also very stable in air in connection, toxicity is low；Its catalyst has higher hydrophobicity, Yi Jiqiang
Hydro-thermal and mechanical stability.
Given this, it is desirable to provide a kind of skill for preparing the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine
Art.
Summary of the invention
Technical problem to be solved by the present invention lies in provide a kind of functionalized order mesoporous organosilicon of N- heterocycle carbine
Pd catalyst.
Its technical problem to be solved can be implemented by the following technical programs.
A kind of functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine, is prepared using following steps:
(1), firstly, substitution reaction, which occurs, with 2,6-DIPA and IX generates the iodo- 2,6-DIPA of 4-；
The IX is lodine chloride, Iodide Bromide or iodine；
(2), the iodo- 2,6-DIPA of 4- and glyoxal reaction then, obtained using step (1) generates bis- (4-
I-2,6- diisopropyl phenyl) diaza butadiene；
(3), generate bis- (4-I-2,6- diisopropyl phenyl) diaza butadiene again with trifluoro-methane sulfonic acid silver and spy
Valeric acid chloromethyl ester, or bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- of 1,3- are generated with zinc chloride and paraformaldehyde
Salt；
(4), again with bis- (acetonitriles) (1,5- cyclo-octadiene) tetrafluoride rhodium as catalyst, 1,3- bis- (iodo- 2, the 6- bis- of 4- is different
Propyl phenyl) -1H- imidazoles -3- salt reacted with triethoxysilane generate bis- (the 4- triethoxy first of IPr function silicon source 1,3-
Silylation -2,6- diisopropyl phenyl) -1H- imidazoles -3- salt；
(5), then 1,2- bis- (triethoxy silicon substrate) ethane (BTFE) skeleton silicon source is added to dissolved with P123 and chlorination
In the dilute hydrochloric acid solution of sodium, copolymerization is reacted with IPr function silicon source；
(6), by step (5) resulting reaction solution in polytetrafluoroethylene (PTFE) high pressure water heating kettle, aging；
(7), template, dry NHC@PMO carrier are removed to step (6) resulting materials；
(8), it by NHC@PMO carrier, palladium chloride, potassium carbonate, is reacted in 3- chloropyridine solution, obtains N- heterocycle carbine official
The order mesoporous organosilicon Pd catalyst Pd-NHC@PMO of energyization.
As a further improvement of the present invention,
In the preparation of the iodo- 2,6-DIPA of step (1) 4-, solvent is methanol, methylene chloride, 1,2- dichloroethanes
Or anhydrous ether；Reaction temperature is room temperature, reaction time 18-24h；
In the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of 4-) the diaza butadiene of step (2), solvent is methanol, dichloro
Methane, 1,2- dichloroethanes or tetrahydrofuran, reaction temperature are 40-85 DEG C, reaction time 10-14h；
Step (3) 1, in the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- salt of 3-, solvent is first
Alcohol, methylene chloride, dichloroethanes or tetrahydrofuran, reaction temperature are 30-90 DEG C, reaction time 10-24h；
The system of bis- (4- triethoxysilyl -2,6- the diisopropyl phenyl) -1H- imidazoles -3- salt of step (4) 1,3-
In standby, solvent is toluene, n,N-Dimethylformamide or dimethyl sulfoxide, and reaction temperature is 70-100 DEG C, reaction time 8-
12h；
The resulting IPr function silicon source of a dropping step (4), mixing speed 300-600r/min, reaction time in step (5)
Substance withdrawl syndrome for 18-36h, dilute hydrochloric acid accounts for silicon source in 0.2-3mol/L, BTEE skeleton silicon source and IPr function silicon source respectively
The molar fraction ratio of total amount is 88-92% and 8-12%；
Aging temperature is 100-110 DEG C, time 22-28h in step (6), and vacuum drying temperature is 40-50 after suction filtration
DEG C, time 5-8h；
Step (7), which removes template agent removing, to be stirred in the solution of ethyl alcohol and concentrated hydrochloric acid, is carried out under reflux conditions, when reflux
Between be 20-26h, then be dried in vacuo 8-12h at a temperature of 40-60 DEG C；Or removing template agent removing is in ammonium nitrate and dehydrated alcohol
Mixed solution in stir, temperature is dried in vacuo 8-12h at 60-80 DEG C, time 4-8h, then at a temperature of 40-60 DEG C；
Step (8) reaction carries out under the conditions of nitrogen protection, and temperature is 70-90 DEG C, reaction time 12-15h；Exist again
8-12h is dried in vacuo at a temperature of 40-50 DEG C.
As one of the preferred embodiment of the present invention,
In the preparation of the iodo- 2,6-DIPA of step (1) 4-, IX is lodine chloride, and solvent is methanol or methylene chloride；
In the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of 4-) the diaza butadiene of step (2), solvent is methanol, reaction
Temperature is 70 DEG C；
Step (3) 1, in the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- salt of 3-, solvent two
Chloromethanes, reaction temperature are 50-70 DEG C；
The system of bis- (4- triethoxysilyl -2,6- the diisopropyl phenyl) -1H- imidazoles -3- salt of step (4) 1,3-
In standby, solvent n,N-Dimethylformamide, reaction temperature is 75-85 DEG C；
The resulting IPr function silicon source of a dropping step (4), mixing speed 300-600r/min, reaction time in step (5)
For 24-28h, the substance withdrawl syndrome of dilute hydrochloric acid is 2mol/L, and BTEE skeleton silicon source and IPr function silicon source account for silicon source total amount respectively
Molar fraction ratio be 88-92% and 8-12%.
Another technical problem to be solved by this invention is to provide that a kind of N- heterocycle carbine is functionalized order mesoporous has
The preparation method of machine silicon Pd catalyst.This method adopts the following technical scheme that.
A kind of preparation method of the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine, using following steps:
(1), firstly, substitution reaction, which occurs, with 2,6-DIPA and IX generates the iodo- 2,6-DIPA of 4-；
The IX is lodine chloride, Iodide Bromide or iodine (preferably lodine chloride)；
(2), the iodo- 2,6-DIPA of 4- and glyoxal reaction then, obtained using step (1) generates bis- (4-
I-2,6- diisopropyl phenyl) diaza butadiene；
(3), generate bis- (4-I-2,6- diisopropyl phenyl) diaza butadiene again with trifluoro-methane sulfonic acid silver and spy
Valeric acid chloromethyl ester, or bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- of 1,3- are generated with zinc chloride and paraformaldehyde
Salt；
(4), again with bis- (acetonitriles) (1,5- cyclo-octadiene) tetrafluoride rhodium as catalyst, 1,3- bis- (iodo- 2, the 6- bis- of 4- is different
Propyl phenyl) -1H- imidazoles -3- salt reacted with triethoxysilane generate bis- (the 4- triethoxy first of IPr function silicon source 1,3-
Silylation -2,6- diisopropyl phenyl) -1H- imidazoles -3- salt；
(5), then 1,2- bis- (triethoxy silicon substrate) ethane (BTFE) skeleton silicon source is added to dissolved with P123 and chlorination
In the dilute hydrochloric acid solution of sodium, copolymerization is reacted with IPr function silicon source；
(6), by step (5) resulting reaction solution in polytetrafluoroethylene (PTFE) high pressure water heating kettle, aging；
(7), template, dry NHC@PMO carrier are removed to step (6) resulting materials；
(8), it by NHC@PMO carrier, palladium chloride, potassium carbonate, is reacted in 3- chloropyridine solution, obtains N- heterocycle carbine official
The order mesoporous organosilicon Pd catalyst Pd-NHC@PMO of energyization.
As the further improvement of the technical program, in the preparation of the iodo- 2,6-DIPA of step (1) 4-, solvent
For methanol, methylene chloride, 1,2- dichloroethanes or anhydrous ether (preferably methanol and methylene chloride)；Reaction temperature is room temperature, instead
It is 18-24h between seasonable.
Also as the further improvement of the technical program, bis- (iodo- 2, the 6- diisopropyl phenyl of 4-) the diaza fourths of step (2)
In the preparation of diene, solvent is that methanol, methylene chloride, 1,2- dichloroethanes or tetrahydrofuran (preferably methanol), reaction temperature are
40-85 DEG C (preferably 70 DEG C), reaction time 10-14h.
Also as the further improvement of the technical program, step (3) 1, bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- of 3-
In the preparation of imidazoles -3- salt, solvent is methanol, methylene chloride, dichloroethanes or tetrahydrofuran (preferably methylene chloride), reaction
Temperature is 30-90 DEG C (preferably 50-70 DEG C), reaction time 10-24h.
Further improvement equally as the technical program, step (4) 1, bis- (the 4- triethoxysilyls -2,6- of 3-
Diisopropyl phenyl) -1H- imidazoles -3- salt preparation in, solvent be toluene, n,N-Dimethylformamide or dimethyl sulfoxide
(preferably n,N-Dimethylformamide), reaction temperature are 70-100 DEG C (preferably 75-85 DEG C), reaction time 8-12h.
Equally further improvement as the technical program, the resulting IPr function silicon source of a dropping step (4) in step (5),
Mixing speed is 300-600r/min, and the reaction time is 18-36h (preferably 24-28h), and the substance withdrawl syndrome of dilute hydrochloric acid exists
0.2-3mol/L (preferably 3mol/L), the molar fraction ratio that BTEE skeleton silicon source accounts for silicon source total amount with IPr function silicon source respectively are
88-92% and 8-12%.
Equally further improvement as the technical program, aging temperature is 100-110 DEG C in step (6), time 22-
28h, vacuum drying temperature are 40-50 DEG C, time 5-8h.
Equally further improvement as the technical program, it is in the molten of ethyl alcohol and concentrated hydrochloric acid that step (7), which removes template agent removing,
It in liquid, carries out under reflux conditions, return time 20-26h, then be dried in vacuo 8-12h at a temperature of 40-60 DEG C；Or it goes
Template agent removing is in the mixed solution of ammonium nitrate and dehydrated alcohol, and temperature is at 60-80 DEG C, time 4-8h, then at 40-60 DEG C
At a temperature of be dried in vacuo 8-12h.
Further improvement equally as the technical program, step (8) reaction carry out under the conditions of nitrogen protection, and temperature is
70-90 DEG C, reaction time 12-15h；8-12h is dried in vacuo at a temperature of 40-50 DEG C again.
One of preferred embodiment as this preparation method,
In the preparation of the iodo- 2,6-DIPA of step (1) 4-, IX is lodine chloride, and solvent is methanol or methylene chloride；
Reaction temperature is room temperature, reaction time 18-24h；
In the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of 4-) the diaza butadiene of step (2), solvent is methanol, reaction
Temperature is 70 DEG C, reaction time 10-14h；
Step (3) 1, in the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- salt of 3-, solvent two
Chloromethanes, reaction temperature are 50-70 DEG C, reaction time 10-24h；
The system of bis- (4- triethoxysilyl -2,6- the diisopropyl phenyl) -1H- imidazoles -3- salt of step (4) 1,3-
In standby, solvent is n,N-Dimethylformamide, and reaction temperature is 75-85 DEG C, reaction time 8-12h；
The resulting IPr function silicon source of a dropping step (4), mixing speed 300-600r/min, reaction time in step (5)
For 24-28h, the substance withdrawl syndrome of dilute hydrochloric acid is 2mol/L, and BTEE skeleton silicon source and IPr function silicon source account for silicon source total amount respectively
Molar fraction ratio be 88-92% and 8-12%；
Aging temperature is 100-110 DEG C, time 22-28h in step (6), and vacuum drying temperature is 40-50 after suction filtration
DEG C, time 5-8h；
Step (7), which removes template agent removing, to be carried out under reflux conditions, return time is in the solution of ethyl alcohol and concentrated hydrochloric acid
20-26h, then 8-12h is dried in vacuo at a temperature of 40-60 DEG C；Or removing template agent removing is in the mixed of ammonium nitrate and dehydrated alcohol
It closes in solution, temperature is dried in vacuo 8-12h at 60-80 DEG C, time 4-8h, then at a temperature of 40-60 DEG C；
Step (8) reaction carries out under the conditions of nitrogen protection, and temperature is 70-90 DEG C, reaction time 12-15h；Exist again
8-12h is dried in vacuo at a temperature of 40-50 DEG C.
Catalyst by adopting the above technical scheme and preparation method thereof, the imidazoles function modified with 3- chloropyridine and palladium chloride
Ordered mesoporous silicon Pd catalyst (Pd-NHC@PMO) can be changed applied in the Suzuki-Miyaura coupling reaction of aryl chloride.
It is prepared compared with traditional Pd catalyst is only used for the Suzuki-Miyaura coupling reaction of aryl bromide or iodide
Pd-NHC@PMO catalyst has the advantage that
(1), there is very high reactivity in the Suzuki-Miyaura coupling of aryl halide, can also especially answers
In the coupling reaction of aryl chloride；
(2), since the organic moiety introduced in carrier is to carry out self assembly on a molecular scale, so that organic moiety is more equal
It is distributed in the frame of material, rather than is grafted on the hole surface of material evenly；
(3), order mesoporous organosilicon material (NHC-PMO) surface area with higher, the orderly nano pore formed
With lesser diffusional resistance；
(4), there are higher hydrophobicity, stronger hydrothermal stability and mechanical stability, and also very stable in air, poison
Property is low；
(5), catalyst can be applied in the micro- reaction synthesis of X-Cube, and can amplify test, have industrial application
Prospect.
Detailed description of the invention
Make one to a specific embodiment of the invention with reference to the accompanying drawing to be described in detail.
Fig. 1 is preparation and the reaction process of the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine of the present invention
Figure；
Specific embodiment
The present invention provides functionalized order mesoporous organosilicon Pd catalyst of a kind of N- heterocycle carbine and preparation method thereof,
Shown in referring to Fig.1, first synthetic IPr function silicon source, then hydrolyzes copolymerization with BTEE skeleton silicon source in acid condition and is urged
Agent carrier NHC@PMO grafts PdCl2 after forming destination carrier, then after passing through and 3- chloropyridine is coordinated, eventually forms N- heterocycle
The order mesoporous organosilicon Pd catalyst (Pd-NHC@PMO) of Cabbeen functionalization.
The present invention is specifically described below with reference to embodiment, it is necessary to which indicated herein is that the present invention is served only for
Invention is further explained, should not be understood as limiting the scope of the invention.
Embodiment 1
The preparation of the iodo- 2,6- diisopropyl aniline of 4-:
With reference to above-mentioned reaction equation, 11.5mL (55.1mmol) 2,6-DIPA is taken to be dissolved in containing 140mL methanol
In 500mL three-necked flask, the sodium bicarbonate for weighing 13.9g (165.3mmol) is added thereto.In addition 10.5g is weighed
(62.5mmol) lodine chloride is dissolved in the methylene chloride of 140mL, is placed in constant pressure funnel, then it is made slowly to instill three mouthfuls
In flask.It reacts and filters afterwards for 24 hours at room temperature, washed with anhydrous ether to remove solid sodium chloride, and filter vacuum is condensed into
Then the saturated sodium thiosulfate solution of 300mL is added in dark red oil, stir 1h.Extracted again with 3 × 200mL anhydrous ether
It takes, merges organic solution, and with the dry 2h of anhydrous sodium sulfate, after filtering, be concentrated in vacuo filtrate, cross column (PE:EA=25:1)
To dark red oil product 15.7g, yield 73%.
Embodiment 2
The preparation of the iodo- 2,6- diisopropyl aniline of 4-:
With reference to above-mentioned reaction equation, 5.3mL (25mmol) 2,6-DIPA is taken to be dissolved in containing 100mL anhydrous ether
In 250mL three-necked flask, weighs 6.3g (165.3mmol) sodium bicarbonate and be added thereto, separately weigh 7.6g (30mmol) iodine
It is slowly added thereto.It filters, is washed with anhydrous ether to remove sodium iodide solid after reacting 15h at room temperature, and by filter vacuum
It is condensed into dark red oil, the saturated sodium thiosulfate of 300mL is then added, stirs 2h.Again with 3 × 200mL anhydrous ether
Extraction, merges organic solution, and with the dry 2h of anhydrous sodium sulfate, after filtering, is concentrated in vacuo filtrate, crosses column (PE:EA=25:1)
Obtain dark red oil product 3.78g, yield 50%.
Embodiment 3
The preparation of bis- (the iodo- 2,6- diisopropyl phenyl of 4-) diaza butadiene:
With reference to above-mentioned reaction equation, weighs the iodo- 2,6-DIPA of 4.04g (13.3mmol) 4- and be dissolved in containing 20mL
In two mouthfuls of flasks of the 100mL of methanol, two drop formic acid are added dropwise as catalyst, is heated to flowing back at 70 DEG C, measures 0.92mL
(8mmol) glyoxal is dissolved in the methanol of 10mL, instills it slowly in flask, is stirred 8 hours.Then it is obtained by filtration one
Divide bright yellow solid powder, is dissolved after residual filtrate vacuum concentration with anhydrous ether, then in petroleum ether and methyl tertiary butyl ether(MTBE)
It is middle to cross column, obtain another part glassy yellow powder, gross product 4.07g, yield 97%.
Embodiment 4
The synthesis of bis- (the iodo- 2,6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- trifluoro-methanyl sulfonates of 1,3-:
With reference to above-mentioned reaction equation, bis- (iodo- 2, the 6- diisopropyl phenyl of 4-) diaza fourths of 1.1g (1.75mmol) are weighed
Diene is dissolved completely in the 100mL flask containing 20mL methylene chloride, weighs the chloromethyl pivalate of 448mg (2.98mmol)
It being added thereto, is then wrapped with masking foil, the silver trifluoromethanesulfonate of 675mg (2.63mmol) is added thereto, 60 DEG C are heated to,
Reflux for 24 hours, after being cooled to room temperature, is filtered to remove impurity silver nitride precipitation, is then concentrated in vacuo filtrate, products therefrom in methanol and
It is recrystallized under conditions of anhydrous ether, obtains khaki crystalline product 975mg, yield 60.8%.
Embodiment 5
The synthesis of bis- (the iodo- 2,6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- hydrochlorides of 1,3-:
With reference to above-mentioned reaction equation, bis- (iodo- 2, the 6- diisopropyl phenyl of 4-) the diaza fourths two of 1.1g (1.75mmol) are weighed
Alkene, 245mg (1.8mmol) anhydrous zinc chloride are dissolved completely in the 250mL flask containing 125mL tetrahydrofuran, are then added
57mg paraformaldehyde is added dropwise 1.8mL anhydrous hydrogen chloride (4.0M is in Isosorbide-5-Nitrae-dioxane), is heated to 70 DEG C, back flow reaction
12h is extracted after vacuum concentration after cooling down room temperature, and filtrate dries 2h with anhydrous magnesium sulfate, is then filtered, and is concentrated in vacuo, and gained produces
Object recrystallizes under conditions of ethyl acetate and petroleum ether, obtains khaki crystalline product 470mg, yield 39.7%.
Embodiment 6
Bis- (4- triethoxysilyl -2,6- the diisopropyl phenyl) -1H- imidazoles -3- trifluoromethayl sulfonic acids of 1,3-
The synthesis of salt:
With reference to above-mentioned reaction equation, by bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- miaows of 890mg (1.13mmol) 1,3-
Azoles -3- trifluoro-methanyl sulfonate and 31mg (0.081mmol)) bis- (acetonitriles) (1,5- cyclo-octadiene) tetrafluoride rhodium pours into
In bis- mouthfuls of flasks of 100mL, the n,N-Dimethylformamide of 10mL is added, is uniformly mixed it, then weighs 1.85g
(11.27mmol) triethoxysilane and 1.43g (14.09mmol) triethylamine are dissolved in the N,N-dimethylformamide of 10mL
In, it is slowly added dropwise, temperature is increased to 80 DEG C, cools down after being stirred to react 10h, after vacuum concentration, is dissolved in 30mL methylene chloride, slowly
Water extraction is added in slow filtering, takes the dry 1h of organic phase anhydrous sodium sulfate, filters, then be concentrated in vacuo after stirring, obtain khaki
Brown product 900mg, yield 92.3%.
Embodiment 7
The synthesis of bis- (4- triethoxysilyl -2,6- the diisopropyl phenyl) -1H- imidazoles -3- hydrochlorides of 1,3-:
With reference to above-mentioned reaction equation, by bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles-of 470mg (0.6mmol) 1,3-
3- hydrochloride and 17mg (0.045mmol)) bis- (acetonitriles) (1,5- cyclo-octadiene) tetrafluoride rhodium pours into bis- mouthfuls of flasks of 100mL
In, the n,N-Dimethylformamide of 10mL is added, is uniformly mixed it, then weighs 978mg (5.95mmol) triethoxysilicane
Alkane and 753mg (7.44mmol) triethylamine are dissolved in the n,N-Dimethylformamide of 10mL, are slowly added dropwise, temperature is increased to 80
DEG C, it is stirred to react cooling after 10h, is dissolved in 30mL methylene chloride after vacuum concentration, slowly filters, water extraction is added, takes organic
Mutually with the dry 3h of anhydrous sodium sulfate, is filtered after stirring, then be concentrated in vacuo, obtain khaki brown product 170mg, yield is
40%.
Embodiment 8
The preparation of NHC@PMO carrier 1. material:
With reference to above-mentioned reaction equation, 0.78g P123 is taken, 1.64g sodium chloride is dissolved in 4.5mL (2M) hydrochloric acid and 10.5mL H20
Mixed solution in, be placed in 40 DEG C of water baths, stir 1h, revolving speed 600r/min.12.5mL H20 and 4.5mL (2M) are taken again
Hydrochloric acid pours into mixed solution, stirs 10min, adds 1.86g1,2- bis- (triethoxy silicon substrate) ethane (BTEE) framework silicon
Source, 60 drop per minute, revolving speed 500r/min stir 1h.Continue that 805mg (0.58mmol) IPr function silicon source is added dropwise, per minute
60 drops, revolving speed 600r/min, stirring is for 24 hours.After, reflection mixture is transferred in polytetrafluoroethylene (PTFE) high pressure water heating kettle,
Static reaction is for 24 hours in 110 DEG C of baking oven.It takes out from water heating kettle, after cooling, is filtered, then washed with deionized water and ethyl alcohol
It washs, is finally placed in 50 DEG C of vacuum ovens, dry 6h.Then with 240mL dehydrated alcohol and 160mg ammonium nitrate to solid powder
Soxhlet extraction is carried out, after 6h, filters, with deionized water and ethanol washing solid powder, is finally placed in 50 DEG C of vacuum drying, obtains
Pale yellow powder, that is, intended catalyzed agent carrier (NHC PMO) 1.74g.
Embodiment 9
The preparation of NHC@PMO carrier 2. material:
With reference to above-mentioned reaction equation, 430mg P123 is taken, 923mg sodium chloride is dissolved in the mixing of 2mL (2M) hydrochloric acid and 5mL H20
It in solution, is placed in 40 DEG C of water baths, stirs 1h, revolving speed 600r/min.7mL H20 and 16mL (2M) hydrochloric acid is taken to pour into it again
Mixed solution stirs 10min, adds 1.05g1,2- bis- (triethoxy silicon substrate) ethane (BTFE) skeleton silicon source, and per minute 60
Drop, revolving speed 500r/min stir 1h.Take 3mL methanol dissolution 420mg (0.59mmol) IPr function silicon source, per minute 60
Drop, revolving speed 600r/min, stirring is for 24 hours.After, reflection mixture is transferred in polytetrafluoroethylene (PTFE) high pressure water heating kettle, 110
DEG C baking oven in static reaction for 24 hours.From taken out in water heating kettle it is cooling after, filtered, then with deionized water and ethanol washing, most
It is placed in 50 DEG C of vacuum ovens, dry 6h.Then solid powder is carried out with 240mL dehydrated alcohol and 160mg ammonium nitrate
Soxhlet extraction after 6h, filters, with deionized water and ethanol washing solid powder, is finally placed in 50 DEG C of vacuum drying, obtains yellowish
Color powder, that is, intended catalyzed agent carrier (NHC PMO) has 680mg.
Embodiment 10
The preparation of the functionalized order mesoporous Pd catalyst (Pd-NHC@PMO) of N- heterocycle carbine:
With reference to above-mentioned reaction equation, take 650mg NHC@PMO carrier, 20mg palladium chloride and 41mg potassium carbonate in the circle of 25mL
In the flask of bottom, 8mL3- chloropyridine is then added, under N2 protection, is warming up to 80 DEG C, is filtered after being stirred to react 15h, with dissolved with few
Isosorbide-5-Nitrae-dioxane solvent washing of 3- chloropyridine, vacuum concentration are measured, 50 DEG C of vacuum drying 10h obtain N- heterocycle carbine function
Order mesoporous Pd catalyst (the Pd-NHC@PMO) 690mg changed.
Claims (13)
1. a kind of functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine, which is characterized in that use following steps system
It is standby to form:
(1), firstly, substitution reaction, which occurs, with 2,6-DIPA and IX generates the iodo- 2,6-DIPA of 4-；It is described
IX is lodine chloride, Iodide Bromide or iodine；
(2), the iodo- 2,6-DIPA of 4- and glyoxal reaction then, obtained using step (1) generate it is bis- (4-I-2,
6- diisopropyl phenyl) diaza butadiene；
(3), generate bis- (4-I-2,6- diisopropyl phenyl) diaza butadiene again with trifluoro-methane sulfonic acid silver and pivalic acid
Chloromethyl ester, or bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- salt of 1,3- are generated with zinc chloride and paraformaldehyde；
(4), again with bis- (acetonitriles) (1,5- cyclo-octadiene) tetrafluoride rhodium as catalyst, 1,3- bis- (iodo- 2,6- diisopropyls of 4-
Phenyl) -1H- imidazoles -3- salt reacted with triethoxysilane generate bis- (the 4- triethoxy-silicanes of IPr function silicon source 1,3-
Base -2,6- diisopropyl phenyl) -1H- imidazoles -3- salt；
(5), then 1,2- bis- (triethoxy silicon substrate) ethane (BTEE) skeleton silicon source is added to dissolved with P123 and sodium chloride
In dilute hydrochloric acid solution, copolymerization is reacted with IPr function silicon source；
(6), by step (5) resulting reaction solution in polytetrafluoroethylene (PTFE) high pressure water heating kettle, aging is dry after suction filtration；
(7), template is removed to step (6) resulting materials, re-dry obtains NHC@PMO carrier；
(8), it by NHC@PMO carrier, palladium chloride, potassium carbonate, is reacted in 3- chloropyridine solution, obtains N- heterocycle carbine functionalization
Order mesoporous organosilicon Pd catalyst Pd-NHC@PMO.
2. the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine according to claim 1, which is characterized in that
In the preparation of the iodo- 2,6-DIPA of step (1) 4-, solvent is methanol, methylene chloride, 1,2- dichloroethanes or nothing
Water ether；Reaction temperature is room temperature, reaction time 18-24h；
In the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of 4-) the diaza butadiene of step (2), solvent be methanol, methylene chloride,
1,2- dichloroethanes or tetrahydrofuran, reaction temperature are 40-85 DEG C, reaction time 10-14h；
Step (3) 1, in the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- salt of 3-, solvent is methanol, two
Chloromethanes, dichloroethanes or tetrahydrofuran, reaction temperature are 30-90 DEG C, reaction time 10-24h；
The preparation of bis- (4- triethoxysilyl -2,6- the diisopropyl phenyl) -1H- imidazoles -3- salt of step (4) 1,3-
In, solvent is toluene, n,N-Dimethylformamide or dimethyl sulfoxide, and reaction temperature is 70-100 DEG C, reaction time 8-
12h；
The resulting IPr function silicon source of a dropping step (4), mixing speed 300-600r/min, reaction time are in step (5)
18-36h, for the substance withdrawl syndrome of dilute hydrochloric acid in 0.2-3mol/L, it is total that BTEE skeleton silicon source with IPr function silicon source accounts for silicon source respectively
The molar fraction ratio of amount is 88-92% and 8-12%；
Aging temperature is 100-110 DEG C, time 22-28h in step (6), and the vacuum drying temperature after aging is 40-50 DEG C,
Time is 5-8h；
Step (7), which removes template agent removing, to be stirred under reflux conditions, return time 20- in the solution of ethyl alcohol and concentrated hydrochloric acid
26h, then 8-12h is dried in vacuo at a temperature of 40-60 DEG C；Or it is molten in the mixing of ammonium nitrate and dehydrated alcohol for removing template agent removing
It is stirred in liquid, temperature is dried in vacuo 8-12h at 60-80 DEG C, time 4-8h, then at a temperature of 40-60 DEG C；
Step (8) reaction carries out under the conditions of nitrogen protection, and temperature is 70-90 DEG C, reaction time 12-15h；Again in 40-50
8-12h is dried in vacuo at a temperature of DEG C.
3. the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine according to claim 1 or claim 2, feature exist
In,
In the preparation of the iodo- 2,6-DIPA of step (1) 4-, IX is lodine chloride, and solvent is methanol or methylene chloride；
In the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of 4-) the diaza butadiene of step (2), solvent is methanol, reaction temperature
It is 70 DEG C；
Step (3) 1, in the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- salt of 3-, solvent is dichloromethane
Alkane, reaction temperature are 50-70 DEG C；
The preparation of bis- (4- triethoxysilyl -2,6- the diisopropyl phenyl) -1H- imidazoles -3- salt of step (4) 1,3-
In, solvent n,N-Dimethylformamide, reaction temperature is 75-85 DEG C；
The resulting IPr function silicon source of a dropping step (4), mixing speed 300-600r/min, reaction time are in step (5)
24-28h, the substance withdrawl syndrome of dilute hydrochloric acid are 2mol/L, and BTEE skeleton silicon source and IPr function silicon source account for silicon source total amount respectively
Molar fraction ratio is 88-92% and 8-12%.
4. a kind of preparation method of the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine, which is characterized in that use
Following steps:
(1), firstly, substitution reaction, which occurs, with 2,6-DIPA and IX generates the iodo- 2,6-DIPA of 4-；It is described
IX is lodine chloride, Iodide Bromide or iodine；
(2), the iodo- 2,6-DIPA of 4- and glyoxal reaction then, obtained using step (1) generate it is bis- (4-I-2,
6- diisopropyl phenyl) diaza butadiene；
(3), generate bis- (4-I-2,6- diisopropyl phenyl) diaza butadiene again with trifluoro-methane sulfonic acid silver and pivalic acid
Chloromethyl ester, or bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- salt of 1,3- are generated with zinc chloride and paraformaldehyde；
(4), again with bis- (acetonitriles) (1,5- cyclo-octadiene) tetrafluoride rhodium as catalyst, 1,3- bis- (iodo- 2,6- diisopropyls of 4-
Phenyl) -1H- imidazoles -3- salt reacted with triethoxysilane generate bis- (the 4- triethoxy-silicanes of IPr function silicon source 1,3-
Base -2,6- diisopropyl phenyl) -1H- imidazoles -3- salt；
(5), then 1,2- bis- (triethoxy silicon substrate) ethane (BTFE) skeleton silicon source is added to dissolved with P123 and sodium chloride
In dilute hydrochloric acid solution, copolymerization is reacted with IPr function silicon source；
(6), by step (5) resulting reaction solution in polytetrafluoroethylene (PTFE) high pressure water heating kettle, aging；
(7), template, dry NHC@PMO carrier are removed to step (6) resulting materials；
(8), it by NHC@PMO carrier, palladium chloride, potassium carbonate, is reacted in 3- chloropyridine solution, obtains N- heterocycle carbine functionalization
Order mesoporous organosilicon Pd catalyst Pd-NHC@PMO.
5. the preparation method of the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine according to claim 4,
It is characterized in that, in the preparation of the iodo- 2,6-DIPA of step (1) 4-, solvent is methanol, methylene chloride, 1,2-, bis- chloroethene
Alkane or anhydrous ether；Reaction temperature is room temperature, reaction time 18-24h.
6. the preparation method of the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine according to claim 4,
It is characterized in that, in the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of 4-) the diaza butadiene of step (2), solvent is methanol, dichloro
Methane, 1,2- dichloroethanes or tetrahydrofuran, reaction temperature are 40-85 DEG C, reaction time 10-14h.
7. the preparation method of the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine according to claim 4,
It is characterized in that, step (3) 1, in the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- salt of 3-, solvent is first
Alcohol, methylene chloride, dichloroethanes or tetrahydrofuran, reaction temperature are 30-90 DEG C, reaction time 10-24h.
8. the preparation method of the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine according to claim 4,
It is characterized in that, step (4) 1, bis- (4- triethoxysilyl -2,6- diisopropyl phenyl) -1H- imidazoles -3- salt of 3-
In preparation, solvent is toluene, n,N-Dimethylformamide or dimethyl sulfoxide, and reaction temperature is 70-100 DEG C, and the reaction time is
8-12h。
9. the preparation method of the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine according to claim 4,
It is characterized in that, the resulting IPr function silicon source of a dropping step (4) in step (5), mixing speed 300-600r/min, when reaction
Between be 18-36h, the substance withdrawl syndrome of dilute hydrochloric acid accounts for silicon in 0.2-3mol/L, BTEE skeleton silicon source and IPr function silicon source respectively
The molar fraction ratio of source total amount is 88-92% and 8-12%.
10. the preparation method of the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine according to claim 4,
It is characterized in that, aging temperature is 100-110 DEG C, time 22-28h in step (6), and vacuum drying temperature is 40-50 DEG C, the time
For 5-8h.
11. the preparation method of the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine according to claim 4,
It is characterized in that, step (7), which removes template agent removing, to be stirred under reflux conditions, return time in the solution of ethyl alcohol and concentrated hydrochloric acid
For 20-26h, then at a temperature of 40-60 DEG C it is dried in vacuo 8-12h；Or removing template agent removing is in ammonium nitrate and dehydrated alcohol
It is stirred in mixed solution, temperature is dried in vacuo 8-12h at 60-80 DEG C, time 4-8h, then at a temperature of 40-60 DEG C.
12. the preparation method of the functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine according to claim 4,
It is characterized in that, step (8) reaction carries out under the conditions of nitrogen protection, and temperature is 70-90 DEG C, reaction time 12-15h；Exist again
8-12h is dried in vacuo at a temperature of 40-50 DEG C.
13. being urged according to the functionalized order mesoporous organosilicon Pd of N- heterocycle carbine described in any claim in claim 4-12
The preparation method of agent, which is characterized in that
In the preparation of the iodo- 2,6-DIPA of step (1) 4-, IX is lodine chloride, and solvent is methanol or methylene chloride；Reaction
Temperature is room temperature, reaction time 18-24h；
In the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of 4-) the diaza butadiene of step (2), solvent is methanol, reaction temperature
It is 70 DEG C, reaction time 10-14h；
Step (3) 1, in the preparation of bis- (iodo- 2, the 6- diisopropyl phenyl of the 4-) -1H- imidazoles -3- salt of 3-, solvent is dichloromethane
Alkane, reaction temperature are 50-70 DEG C, reaction time 10-24h；
The preparation of bis- (4- triethoxysilyl -2,6- the diisopropyl phenyl) -1H- imidazoles -3- salt of step (4) 1,3-
In, solvent is n,N-Dimethylformamide, and reaction temperature is 75-85 DEG C, reaction time 8-12h；
The resulting IPr function silicon source of a dropping step (4), mixing speed 300-600r/min, reaction time are in step (5)
24-28h, the substance withdrawl syndrome of dilute hydrochloric acid are 2mol/L, and BTEE skeleton silicon source and IPr function silicon source account for silicon source total amount respectively
Molar fraction ratio is 88-92% and 8-12%；
Aging temperature is 100-110 DEG C, time 22-28h in step (6), and vacuum drying temperature is 40-50 DEG C after suction filtration, when
Between be 5-8h；
Step (7), which removes template agent removing, to be carried out under reflux conditions, return time 20- in the solution of ethyl alcohol and concentrated hydrochloric acid
26h, then 8-12h is dried in vacuo at a temperature of 40-60 DEG C；Or it is molten in the mixing of ammonium nitrate and dehydrated alcohol for removing template agent removing
In liquid, temperature is dried in vacuo 8-12h at 60-80 DEG C, time 4-8h, then at a temperature of 40-60 DEG C；
Step (8) reaction carries out under the conditions of nitrogen protection, and temperature is 70-90 DEG C, reaction time 12-15h；Again in 40-50
8-12h is dried in vacuo at a temperature of DEG C.
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