CN114507259A - Transition metal iridium complex photocatalyst and preparation method and application thereof - Google Patents
Transition metal iridium complex photocatalyst and preparation method and application thereof Download PDFInfo
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- CN114507259A CN114507259A CN202210090486.7A CN202210090486A CN114507259A CN 114507259 A CN114507259 A CN 114507259A CN 202210090486 A CN202210090486 A CN 202210090486A CN 114507259 A CN114507259 A CN 114507259A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 65
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 63
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 32
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 36
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 16
- LPQZERIRKRYGGM-UHFFFAOYSA-N tert-butyl pyrrolidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCC1 LPQZERIRKRYGGM-UHFFFAOYSA-N 0.000 claims abstract description 12
- YWNJQQNBJQUKME-UHFFFAOYSA-N 2-bromo-5-methylpyridine Chemical compound CC1=CC=C(Br)N=C1 YWNJQQNBJQUKME-UHFFFAOYSA-N 0.000 claims abstract description 9
- LBUNNMJLXWQQBY-UHFFFAOYSA-N 4-fluorophenylboronic acid Chemical compound OB(O)C1=CC=C(F)C=C1 LBUNNMJLXWQQBY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000007530 organic bases Chemical class 0.000 claims abstract description 8
- FFOMEQIMPYKURW-UHFFFAOYSA-N 4-(trifluoromethyl)-2-[4-(trifluoromethyl)pyridin-2-yl]pyridine Chemical compound FC(F)(F)C1=CC=NC(C=2N=CC=C(C=2)C(F)(F)F)=C1 FFOMEQIMPYKURW-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZHMXQYAUGQASQM-UHFFFAOYSA-N 5-(trifluoromethyl)-2-[5-(trifluoromethyl)pyridin-2-yl]pyridine Chemical compound N1=CC(C(F)(F)F)=CC=C1C1=CC=C(C(F)(F)F)C=N1 ZHMXQYAUGQASQM-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 ammonium hexafluorophosphate Chemical compound 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229940125904 compound 1 Drugs 0.000 claims description 9
- 229940125782 compound 2 Drugs 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 230000029936 alkylation Effects 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- YOLNUNVVUJULQZ-UHFFFAOYSA-J iridium;tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ir] YOLNUNVVUJULQZ-UHFFFAOYSA-J 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- IOFXPWHYYTZRAK-UHFFFAOYSA-M dibutyl phosphate;tetrabutylazanium Chemical compound CCCCOP([O-])(=O)OCCCC.CCCC[N+](CCCC)(CCCC)CCCC IOFXPWHYYTZRAK-UHFFFAOYSA-M 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims 8
- 239000007806 chemical reaction intermediate Substances 0.000 claims 3
- 239000000126 substance Substances 0.000 claims 2
- 239000003446 ligand Substances 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 3
- 150000002504 iridium compounds Chemical class 0.000 abstract description 2
- 238000004440 column chromatography Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- IZPYBIJFRFWRPR-UHFFFAOYSA-N tert-butyl pyrrole-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1C=CC=C1 IZPYBIJFRFWRPR-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VTTPYOSNXQHZFA-UHFFFAOYSA-N 2-pyridin-2-yl-3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1C1=CC=CC=N1 VTTPYOSNXQHZFA-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- SHGAZHPCJJPHSC-YCNIQYBTSA-N all-trans-retinoic acid Chemical compound OC(=O)\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C SHGAZHPCJJPHSC-YCNIQYBTSA-N 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
-
- 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
- B01J31/1805—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 the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/46—C-H or C-C activation
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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
- 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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Abstract
The invention discloses a transition metal iridium complex photocatalyst and a preparation method and application thereof, wherein the molecular formula of the transition metal iridium complex photocatalyst is C36H26F14IrN4P, the synthesis method comprises the steps of taking an intermediate I formed by reacting 2-bromo-5-methylpyridine with 4-fluorobenzeneboronic acid as a ligand, performing coordination reaction with an iridium compound to form an intermediate II, reacting with ligand 4,4 '-bis (trifluoromethyl) -2, 2' -bipyridine or 5,5 '-bis (trifluoromethyl) -2, 2' -bipyridine to obtain an intermediate III, and finally reacting with an ammonium hexafluorophosphate aqueous solution to prepare the intermediate IIIThus obtaining the product. Although the photocatalyst has more synthesis steps, the complicated process of column chromatography separation and purification is not needed, and the yield of the photocatalyst is high. The photocatalyst is applied to an alkylation reaction taking tetrahydrofuran or N-Boc pyrrolidine as a substrate, the alkylation reaction is carried out in the presence of a visible light source and weak organic base, the photocatalytic efficiency is high, the yield of an addition product is high, and the photocatalyst is an excellent photocatalyst worthy of popularization.
Description
Technical Field
The invention belongs to the technical field of synthesis and application of transition metal complexes, and particularly relates to a transition metal iridium complex photocatalyst as well as a preparation method and application thereof.
Background
Photocatalytic alkylation reactions have the advantages of being green, efficient, safe and the like, provide a more convenient alternative method for the traditional alkylation process, have attracted wide attention in organic chemistry, and have reported a number of important reactions, such as cross-coupling reactions, -amino functionalization, cycloaddition reactions, ATRA reactions or fluorination reactions and the like. The transition metal catalyst is combined with photocatalysis, electrons shuttle back and forth between a substrate and an intermediate when being excited by light, or the visible light absorbs the photocatalyst to selectively transfer energy, so that the current free radical chemical process is expected to be improved, and a new way is opened for exploring novel reaction species.
The photocatalyst represented by the iridium complex has excellent catalytic performance and is widely concerned by people. When the photocatalyst formed by related transition metal and fluorine-containing ligand is applied to the alkylation reaction of ethylene compounds, a result superior to other photocatalysts can be obtained (Wan-Fa Tian, et al, adv. Synth. Catal.2020,362, 1-8; Choi GJ, et al, Nature 2016,539, 268-. However, the related iridium complexes are single in variety and not very excellent in performance, and each catalyst can only carry out catalytic alkylation addition on one or more related compounds. Most iridium catalysts need to be treated by methods such as column treatment, so that the method is complex and consumes a large amount of manpower and material resources. For example, DuPont research team synthesizes organic metal iridium complex (Grushin V.V., et al, chem. Commun.,2001, 1494-one 1495) under the catalysis of a small amount of silver triflate, but the iridium complex synthesized by the method can only be the same as a ligand, and because the ligand is used as a reaction raw material and a solvent at the same time, the cost is high, and the method is not beneficial to popularization. Therefore, the novel iridium complex catalyst has very high application value in the alkylation reaction of various ethylene compounds.
Disclosure of Invention
The invention aims to disclose a preparation method and application of an iridium complex photocatalyst with photocatalytic performance.
A transition metal iridium complex photocatalyst with a structural molecular formula of C36H26F14IrN4P has a structural formula shown as formula IV:
wherein R is1、R2Are H and CF, respectively3Or are each CF3And H.
The preparation method of the transition metal iridium complex photocatalyst is characterized in that an intermediate I formed by the reaction of 2-bromo-5-methylpyridine and 4-fluorobenzeneboronic acid is taken as a ligand, the ligand reacts with an iridium compound to form an intermediate II through a coordination reaction, and then the intermediate II reacts with 4,4 '-bis (trifluoromethyl) -2, 2' -bipyridine or 5,5 '-bis (trifluoromethyl) -2, 2' -bipyridine to prepare the transition metal iridium complex photocatalyst; the preparation method comprises the following steps:
1) under the protection of inert gas, adding an organic solvent A and water into a mixture of sodium carbonate, 2-bromo-5-methylpyridine, 4-fluorobenzeneboronic acid and a palladium catalyst, heating, stirring, refluxing and reacting, cooling reaction liquid after the reaction is finished, and carrying out post-treatment on the reaction liquid to obtain an intermediate I.
2) Under the protection of inert gas, dissolving the intermediate I prepared in the step 1) and iridium trichloride hydrate in an organic solvent B, heating, stirring, refluxing, reacting, cooling after the reaction is finished, filtering, washing and drying to obtain an intermediate II.
3) Under the protection of inert gas, dissolving the intermediate II obtained in the step 2) and 4,4 '-bis (trifluoromethyl) -2, 2' -bipyridine or 5,5 '-bis (trifluoromethyl) -2, 2' -bipyridine in an organic solvent C, heating, stirring, refluxing for reaction, cooling after the reaction is finished, and carrying out post-treatment on the reaction liquid to obtain an intermediate III.
4) Adding a solution in which the intermediate III prepared in the step 3) is dissolved into an ammonium hexafluorophosphate aqueous solution, stirring at room temperature for reaction, filtering after the reaction is finished, washing a filter cake with water, dissolving the filter cake with dichloromethane, separating liquid, distilling under reduced pressure to obtain an orange-red solid, dissolving the orange-red solid in acetone, heating and refluxing, adding n-hexane, naturally cooling to separate out a solid, filtering, washing the filter cake with n-hexane, and drying to obtain the transition metal iridium complex photocatalyst.
Wherein R is1、R2Are H and CF, respectively3Or are each CF3And H.
The preparation method of the transition metal iridium complex photocatalyst is characterized in that in the step 1), the palladium catalyst is Pd (dppf) Cl2The organic solvent A is one or a mixture of more than two of 1, 4-dioxane, acetonitrile and tetrahydrofuran in any proportion, and the volume ratio of the organic solvent A to water is 3-6: 1; in the step 1), the feeding proportion of the 2-bromo-5-methylpyridine, the 4-fluorobenzeneboronic acid, the palladium catalyst, the sodium carbonate and the organic solvent A is 0.3-0.9 mol: 0.5-1.0 mol: 0.1-0.15% mol: 0.5-1 mol: 1-1.5L, preferably 0.55-0.6 mol: 0.6-0.7 mol: 0.13 to 0.135 mol percent: 0.8 to 9 mol: 1.2-1.3L.
The preparation method of the transition metal iridium complex photocatalyst is characterized in that in the step 1), the mixed solution is heated to 60-90 ℃, the reflux is carried out for 0.5-2 hours, the mixed solution is cooled to room temperature after the reaction is finished, the solvent is removed through reduced pressure distillation, water and methyl tert-butyl ether are added for liquid separation and extraction, the organic phase is washed by saturated salt water, washed by deionized water, dried by anhydrous sodium sulfate, filtered, and the solvent is removed through reduced pressure distillation.
The preparation method of the transition metal iridium complex photocatalyst is characterized in that in the step 2), the feeding ratio of the intermediate I, the iridium trichloride hydrate and the organic solvent B is 55-70 mmol: 25-30 mmol: 250-400mL, preferably 60-65 mmol: 27-28 mmol: 300-350 mL; in the step 2), the organic solvent B is a mixed solution of ethylene glycol monomethyl ether and water, wherein the volume ratio of the ethylene glycol monomethyl ether to the water is 1.5-6: 1.
The preparation method of the transition metal iridium complex photocatalyst is characterized in that in the step 2), the mixed solution is heated to 75-100 ℃ and reacts for 15-24 hours; after the reaction is finished, cooling to room temperature, filtering, washing with water and methanol in sequence, and drying.
The preparation method of the transition metal iridium complex photocatalyst is characterized in that in the step 3), the feeding ratio of the intermediate II, 4 '-bis (trifluoromethyl) -2, 2' -bipyridine or 5,5 '-bis (trifluoromethyl) -2, 2' -bipyridine to the organic solvent C is 2-6 mmol: 8-15 mmol: 40-80mL, preferably 4-5 mmol: 10-11 mmol: 50-60 mL; the organic solvent C is ethylene glycol, ethanol or methanol.
The preparation method of the transition metal iridium complex photocatalyst is characterized in that in the step 3), the mixed solution is heated to 140-180 ℃ and reacts for 2-8 hours; and cooling to room temperature after the reaction is finished, adding dichloromethane and a NaCl aqueous solution with the mass fraction of 1-3%, separating and extracting, removing the solvent from the organic phase through reduced pressure distillation, and finally crystallizing by using normal hexane.
The preparation method of the transition metal iridium complex photocatalyst is characterized in that in the step 4), the feeding ratio of the intermediate III to ammonium hexafluorophosphate is 7-10 g: 40-50 mmol, preferably 8 g: 45mmol of the total weight of the mixture;
in the step 4), the solvent for dissolving the intermediate 3 is methanol, ethanol or dichloromethane.
The preparation method of the transition metal iridium complex photocatalyst is characterized in that in the step 4), the mixed solution is stirred for 14-20 hours at room temperature, and the volume ratio of acetone to n-hexane added during heating reflux is 1: 1-4.
The application of the transition metal iridium complex photocatalyst in catalyzing C-H alkylation reaction of tetrahydrofuran or N-Boc pyrrolidine is characterized in that a compound 1 is tetrahydrofuran or N-Boc pyrrolidine, the compound 1, a compound 2, the transition metal iridium complex photocatalyst, weak organic base and an organic solvent D are added into a reactor together, stirring reaction is carried out under the conditions of nitrogen atmosphere and illumination, the reaction temperature is 40-60 ℃, the reaction time is 8-15 hours, and an alkylation product of tetrahydrofuran or N-Boc pyrrolidine is generated, and the reaction formula is as follows:
wherein: r is phenyl, p-tolyl, methyl or ethyl.
Further, a blue LED light source is adopted for illumination, and the illumination intensity is 80-120mW/cm2Preferably 100mW/cm2。
The feeding molar ratio of the compound 1 to the compound 2 to the iridium complex to the weak organic base is 1: 3-8: 0.01-0.03: 0.03-0.08, preferably 1:5:0.02:0.05, the weak organic base is one of triethylamine, diisopropylethylamine and tetrabutylammonium dibutyl phosphate, and the organic solvent D is trifluorotoluene.
The invention has the beneficial effects that: the intermediate I formed by 2-bromo-5-methylpyridine and 4-fluorophenylboronic acid is used as a ligand of the photocatalyst, the transition metal iridium complex photocatalyst is prepared with high yield, the preparation method is simple to operate, the synthesis cost is low, the transition metal iridium complex photocatalyst can be applied to alkylation reaction with tetrahydrofuran or N-Boc pyrrolidine as a substrate, the iridium complex is used as the photocatalyst to catalyze C-H activation on the tetrahydrofuran or N-Boc pyrrolidine, the catalytic activity is high, and the yield of an alkylation addition product of the tetrahydrofuran or N-Boc pyrrolidine is high.
Drawings
FIG. 1 shows the NMR detection results of the No. 1 Ir complex photocatalyst prepared in example 1 of the present invention.
Fig. 2 shows the nmr detection result of the No. 2 iridium complex photocatalyst prepared in example 2 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
1) Preparation of intermediate I
Under the protection of nitrogen, 0.58mol of 2-bromo-5-methylpyridine, 0.6mol of 4-fluorobenzeneboronic acid and 1.35mmol of Pd (dppf) Cl2Adding 0.87mol of sodium carbonate into a three-neck flask, and then adding a mixed solution (1.2L) of 1, 4-dioxane and water, wherein the volume ratio of the 1, 4-dioxane to the water is 5: 1; then, the mixed reaction solution was heated to 70 ℃ and refluxed for 1 hour. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solvent was removed by distillation under the reduced pressure. The obtained solid is extracted by water and MTBE liquid separation, an organic phase is washed by saturated saline water and water, dried by anhydrous sodium sulfate, filtered, and distilled under reduced pressure to remove the solvent, so that a white solid intermediate I is obtained for standby, and the yield of the intermediate I is 91.5%.
2) Preparation of intermediate II
Under the protection of nitrogen, adding 28mmol of iridium trichloride hydrate and 62mmol of intermediate I prepared in the step 1) into a three-neck flask, and then adding a mixed solution (300mL) of ethylene glycol monomethyl ether and water, wherein the volume ratio of the ethylene glycol monomethyl ether to the water is 3: 1; the mixed solution is heated to 80 ℃ and refluxed for 20 hours, and solid is separated out. After the reaction is finished, the reaction product is cooled to room temperature, filtered, washed by water and methanol and dried to obtain a yellow solid intermediate II for later use, and the yield of the intermediate II is 90.7%.
3) Preparation of intermediate III
Under the protection of nitrogen, 11mmol of 4,4 '-bis (trifluoromethyl) -2, 2' -bipyridine and 5mmol of the intermediate II prepared in the step 2) are added into a three-neck flask, and then 60mL of ethylene glycol is added; the mixture was heated to 150 ℃ and refluxed for 6 hours. Cooling to room temperature, adding dichloromethane, adding 2% by mass of salt water, and stirring to separate liquid into an organic phase and a water phase; and (3) extracting the water phase for multiple times by using dichloromethane as an extracting agent, combining the organic phases, washing the organic phases with water, removing the solvent by reduced pressure distillation, crystallizing by using n-hexane, and filtering to obtain a yellow solid intermediate III for later use, wherein the yield of the intermediate III is 93.4%.
4) Preparation of No. 1 novel iridium complex photocatalyst
Adding 45mmol ammonium hexafluorophosphate and 80mL water into a three-neck flask, stirring to dissolve, and dropwise adding a methanol solution (80mL) containing an intermediate III, wherein the ratio of the intermediate III to the methanol is 1 g: 10mL, stirred at room temperature for 16 hours. After the reaction is finished, filtering, adding water into a filter cake for washing, adding dichloromethane, separating liquid, and removing the solvent by reduced pressure distillation to obtain an orange-red solid; dissolving the orange-red solid with 100mL of acetone, heating and refluxing, adding 150mL of n-hexane, and naturally cooling to separate out the solid. Filtering, washing a filter cake by normal hexane, and drying to obtain an orange solid, namely the No. 1 novel iridium complex photocatalyst, with the yield of 93%. The product was subjected to nuclear magnetic resonance examination, and the results are shown in fig. 1.
Example 2
Example 2 experimental procedure for the preparation of iridium complex photocatalyst example 1 was repeated except that 4,4 '-bis (trifluoromethyl) -2, 2' -bipyridine in step 3) was changed to an equimolar amount of 5,5 '-bis (trifluoromethyl) -2, 2' -bipyridine and the rest of the procedure was the same as in example 1 to finally obtain a novel iridium complex photocatalyst No. 2. The product was subjected to nuclear magnetic resonance examination, and the results are shown in fig. 2.
Comparative examples 1 to 4
Comparative examples 1-4 experimental procedures for preparation of iridium complex photocatalyst example 1 was repeated except that the compounding ratio of 1, 4-dioxane and water was varied in step 1) (the total volume of the mixed solution of 1, 4-dioxane and water was constant at 1.2L), the other operations were the same as in example 1, and the yield of the intermediate i finally obtained was as shown in table 1:
table 1: yield of product obtained from 1, 4-dioxane and water in different ratios
Examples 3 to 5
Examples 3-5 Experimental procedures for preparation of Iridium Complex photocatalyst example 1 was repeated except that the compounding ratio of ethylene glycol methyl ether and water in step 2) was varied (the total volume of the mixture of ethylene glycol methyl ether and water was constant at 300mL), the rest of the procedure was the same as example 1, and the yield of intermediate II finally obtained was as shown in Table 2
Table 2: yield of products obtained from ethylene glycol monomethyl ether and water in different ratios
Examples 6 to 7
Examples 6 to 7 Experimental procedures for preparation of Iridium complex photocatalyst example 1 was repeated except that the solvent used in the reaction in step 3) was different (the volume of the reaction solvent was constantly 60mL), the operation was the same as in example 1, and the yield of intermediate III finally obtained was as shown in Table 3:
table 3: yield of product obtained from different reaction solvents
Examples 8 to 9
Examples 8 to 9 experimental procedures for preparation of iridium complex photocatalyst example 1 was repeated except that the solvent for dissolving intermediate iii in step 4) was different (the amount of the solvent for dissolving intermediate iii was repeated in example 1), and the rest of the procedure was the same as example 1, and the yield results of the iridium complex photocatalyst finally obtained are shown in table 4:
table 4: yield of product obtained by different solvents for intermediate III
Examples 10 to 13
Examples 10 to 13 experimental procedures for preparing iridium complex photocatalyst example 1 was repeated except that the ratio of acetone to n-hexane added at the time of temperature rise and reflux in step 4) was different (the total volume of acetone and n-hexane was 250mL), the other operations were the same as example 1, and the yield results of the finally prepared iridium complex photocatalyst are shown in table 5:
table 5: yield of products obtained from acetone and n-hexane in different ratios
Application example 1:
the synthesized novel iridium complex photocatalyst is used for the photocatalytic alkylation reaction of N-Boc pyrrolidine or tetrahydrofuran, and the reaction process is as follows: 0.01mol of Compound 1 (i.e., N-Boc pyrrole or tetrahydrofuran) and 0.05mol of Compound 2, as well as 0.0002mol of iridium complex photocatalyst and 0.0005mol of tetrabutylammonium dibutylphosphate, an organic base, were charged into a 200mL reaction flask and allowed to standIt was dissolved in 100mL of trifluorotoluene solvent. Introducing nitrogen to replace air in the reaction bottle, and turning on the illumination by using a blue LED light source (100 mW/cm)2) And naturally raising the temperature to 50 ℃ under the illumination intensity. After 10 hours the light was stopped and cooled to room temperature and the reaction quenched with 250ml of water. The aqueous layer was extracted with ether (3X 200 mL); the combined organic layers were washed with 10% LiCl solution (2X 100mL) and once with saturated brine (100mL), then Na2SO4Drying and distilling off the ether to obtain the alkylated product of N-Boc pyrrole or tetrahydrofuran (i.e. compound 3), the specific reaction equation is as follows: :
wherein: r is phenyl, p-tolyl, methyl or ethyl.
According to the operation process, the compound 1 adopts N-Boc pyrrole, and the compound 2 with different structures is adopted for reaction: when the catalysts were selected as iridium complex No. 1 photocatalyst and iridium complex No. 2 photocatalyst, respectively, the yields of the final alkylated product of N-Boc pyrrole are summarized in tables 6 and 7, respectively.
Table 6: alkylation test results of No. 1 Iridium Complex photocatalyst
Table 7: alkylation test results of No. 2 Iridium Complex photocatalyst
According to the above operation, compound 1 is tetrahydrofuran, and compound 2 with different structure is adopted for reaction: when the catalyst was selected from iridium complex No. 1 photocatalyst and iridium complex No. 2 photocatalyst, the yields of the final alkylated product of tetrahydrofuran were summarized in tables 8 and 9, respectively.
Table 8: alkylation test results of No. 1 iridium complex photocatalyst
Table 9: alkylation test results of No. 2 Iridium Complex photocatalyst
It can be seen that: the No. 2 iridium complex photocatalyst is applied to the alkylation reaction of catalyzing N-Boc pyrrolidine or tetrahydrofuran, and has better catalytic activity. When the substituent in the molecular structure of the compound 2 is p-tolyl, the catalytic reaction result is better.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (10)
1. The transition metal iridium complex photocatalyst is characterized in that the structural molecular formula of the transition metal iridium complex photocatalyst is C36H26F14IrN4P has a structural formula shown as formula IV:
wherein R is1、R2Are H and CF, respectively3Or are each CF3And H.
2. The method for preparing a transition metal iridium complex photocatalyst according to claim 1, comprising the following synthetic steps:
(1) synthesis of reaction intermediate i:
under the protection of inert gas, adding an organic solvent A and water into a mixture of sodium carbonate, 2-bromo-5-methylpyridine, 4-fluorobenzeneboronic acid and a palladium catalyst, heating, stirring, refluxing, reacting, cooling a reaction solution after the reaction is finished, distilling under reduced pressure to remove the solvent, adding water and methyl tert-butyl ether, performing liquid-separation extraction, washing an organic phase with saturated saline solution, washing with deionized water, drying with anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain an intermediate I; wherein the reaction temperature is 60-90 ℃, and the reflux time is 0.5-2 h;
(2) and (3) synthesis of a reaction intermediate II:
under the protection of inert gas, dissolving the intermediate I prepared in the step (1) and iridium trichloride hydrate in an organic solvent B, heating, stirring, refluxing, reacting, cooling after the reaction is finished, filtering, washing with water and methanol in sequence, and drying to obtain an intermediate II;
wherein the reaction temperature is 75-100 ℃, and the reaction time is 15-24 hours;
(3) synthesis of reaction intermediate iii:
under the protection of inert gas, dissolving the intermediate II obtained in the step (2) and 4,4 '-bis (trifluoromethyl) -2, 2' -bipyridine or 5,5 '-bis (trifluoromethyl) -2, 2' -bipyridine in an organic solvent C, heating, stirring, refluxing for reaction, cooling after the reaction is finished, and carrying out post-treatment on a reaction solution to obtain an intermediate III;
(4) final Metal Iridium Complex C36H26F14IrN4Transformation and synthesis of P:
adding a solution in which the intermediate III prepared in the step (3) is dissolved into an ammonium hexafluorophosphate aqueous solution, stirring at room temperature for reaction, filtering after the reaction is finished, washing a filter cake with water, dissolving the filter cake with dichloromethane, separating liquid, distilling under reduced pressure to obtain an orange-red solid, dissolving the orange-red solid in acetone, heating for refluxing, adding n-hexane, naturally cooling to separate out a solid, filtering, washing the filter cake with n-hexane, and drying to obtain the metal iridium complex C34H22F14IrN4P。
3. The method according to claim 2, wherein in the step (1), the palladium catalyst is Pd (dppf) Cl2, the organic solvent A is one or a mixture of two or more of 1, 4-dioxane, acetonitrile and tetrahydrofuran in any proportion, and the volume ratio of the organic solvent A to water is 3-6: 1;
in the step (1), the feeding mol ratio of the 2-bromo-5-methylpyridine to the 4-fluorophenylboronic acid to the palladium catalyst to the sodium carbonate is 0.3-0.9: 0.5-1.0: 0.1% -0.15%: 0.5 to 1;
the ratio of the volume of the organic solvent A to the amount of the substance of 2-bromo-5-methylpyridine is 1 to 1.5L: 0.3-0.9 mol.
4. The method for preparing a transition metal iridium complex photocatalyst according to claim 2, wherein in the step 2), the feeding molar ratio of the intermediate I to the iridium trichloride hydrate is 55-70: 25-30;
the ratio of the volume of the organic solvent B to the amount of the substance of the intermediate I was 250-400 mL: 55-70 mmol;
in the step 2), the organic solvent B is a mixed solution of ethylene glycol monomethyl ether and water, wherein the volume ratio of the ethylene glycol monomethyl ether to the water is 1.5-6: 1.
5. The method for preparing a transition metal iridium complex photocatalyst as claimed in claim 2, wherein in the step 3), the feeding molar ratio of the intermediate II to the 4,4 '-bis (trifluoromethyl) -2, 2' -bipyridine or the 5,5 '-bis (trifluoromethyl) -2, 2' -bipyridine is 2-6: 8-15;
the volume ratio of the organic solvent C to the amount of the intermediate II is 40-80 mL: 2-6mmol, and the organic solvent C is ethylene glycol, ethanol or methanol.
6. The method as claimed in claim 2, wherein in step 3), the mixed solution is heated to 140-180 ℃ for reaction for 2-8 hours; and cooling to room temperature after the reaction is finished, adding dichloromethane and a NaCl aqueous solution with the mass fraction of 1-3%, separating and extracting, removing the solvent from the organic phase through reduced pressure distillation, and finally crystallizing by using normal hexane.
7. The method according to claim 2, wherein in the step 4), the ratio of the mass of the intermediate III to the mass of ammonium hexafluorophosphate is 7-10 g: 40-50 mmol; in the step 4), the solvent for dissolving the intermediate III is methanol, ethanol or dichloromethane.
8. The method for preparing a transition metal iridium complex photocatalyst as claimed in claim 2, wherein in the step 4), the mixed solution is stirred at room temperature for 14-20 hours, and the volume ratio of acetone to n-hexane added during heating reflux is 1: 1-4.
9. The use of the transition metal iridium complex photocatalyst of claim 1 for catalyzing the C-H alkylation of tetrahydrofuran or N-Boc pyrrolidine, wherein compound 1 is tetrahydrofuran or N-Boc pyrrolidine, compound 1, compound 2, the transition metal iridium complex photocatalyst, a weak organic base and an organic solvent D are added into a reactor, and stirred under nitrogen atmosphere and light illumination to form an alkylated product of tetrahydrofuran or N-Boc pyrrolidine, according to the following reaction formula:
wherein: r is phenyl, p-tolyl, methyl or ethyl.
10. The use according to claim 9, wherein the illumination is performed using a blue LED source with an illumination intensity of 80-120mW/cm2Preferably 100mW/cm2；
The feeding molar ratio of the compound 1 to the compound 2 to the iridium complex to the weak organic base is 1: 3-8: 0.01-0.03: 0.03-0.08, preferably 1:5:0.02:0.05, the weak organic base is one of triethylamine, diisopropylethylamine and tetrabutylammonium dibutyl phosphate, and the organic solvent D is trifluorotoluene;
the reaction temperature is 40-60 ℃, and the reaction time is 8-15 hours.
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| CHOI, GILBERT J.ET AL.: "Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 539, no. 7628, pages 268 - 271 * |
| CURTIN, PETER N. ET AL.: "Structure-Activity Correlations Among Iridium(III) Photosensitizers in a Robust Water-Reducing System", INORGANIC CHEMISTRY, vol. 48, no. 22, pages 10498 - 10506 * |
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