CN107803223A - Ferrocene cuprous cluster catalyst for catalyzing C-N coupling reaction and preparation method thereof - Google Patents
Ferrocene cuprous cluster catalyst for catalyzing C-N coupling reaction and preparation method thereof Download PDFInfo
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- CN107803223A CN107803223A CN201711178820.XA CN201711178820A CN107803223A CN 107803223 A CN107803223 A CN 107803223A CN 201711178820 A CN201711178820 A CN 201711178820A CN 107803223 A CN107803223 A CN 107803223A
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- ferrocene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000011669 selenium Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 8
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000003446 ligand Substances 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 238000006555 catalytic reaction Methods 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical class BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- LSDUBRNTSSAWDD-UHFFFAOYSA-N CCC.[Se] Chemical compound CCC.[Se] LSDUBRNTSSAWDD-UHFFFAOYSA-N 0.000 claims description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 2
- WLPXNBYWDDYJTN-UHFFFAOYSA-N 1-bromo-2,3-dimethylbenzene Chemical compound CC1=CC=CC(Br)=C1C WLPXNBYWDDYJTN-UHFFFAOYSA-N 0.000 claims 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims 1
- WALCGGIJOOWJIN-UHFFFAOYSA-N iron(ii) selenide Chemical compound [Se]=[Fe] WALCGGIJOOWJIN-UHFFFAOYSA-N 0.000 claims 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 abstract description 6
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052711 selenium Inorganic materials 0.000 abstract description 6
- 238000004817 gas chromatography Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 229910052714 tellurium Inorganic materials 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 12
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 9
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 150000002460 imidazoles Chemical class 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- -1 aryl carbon Chemical compound 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003346 selenoethers Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004772 tellurides Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
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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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0222—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
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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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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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
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a ferrocenyl cuprous cluster catalyst for catalyzing C-N coupling reaction and a preparation method thereof, the catalyst is a cuprous cluster complex based on a ferrocene selenium/tellurium ether ligand, coupling reaction of iodobenzene and imidazole under an alkaline condition is taken as template reaction, and the yield of a series of cuprous cluster compounds as the catalyst is represented by gas chromatography. The invention also discloses a preparation method of the catalyst. The yield of the series of catalysts at high temperature for six hours is 99%, and no solvent is added, so that the application of the series of catalysts in production is increased. Meanwhile, the method is environment-friendly, and reduces the pollution of the solvent to the environment. In addition, the series of cluster compounds have high stability and can be stored in the air for a long time.
Description
Technical field
The present invention relates to organometallic catalytic field of material technology, more particularly to the two of a kind of catalysis C-N coupling reactions
Luxuriant cuprous cluster catalyst of iron and preparation method thereof.
Background technology
The Liv Ullmann C-N coupling reactions of copper catalysis are to build the most classical, the mostly important method of aryl carbon heterodesmic.Contain
The compound of carbon-heterodesmic (such as C-N, C-O, C-S key etc.) is a kind of important component in organic compound, in life chemistry
Middle C-N, C-O, C-S keys mostly be determine its physiologically active key position, thus small molecule synthesis in carbon-heterodesmic coupling one
It is directly the study hotspot in organic synthesis.How easy, cheap, efficient and green method is used to obtain carbon-heterodesmic,
The always emphasis of scientists concern.It is low to presently, there are severe reaction conditions, catalytic conversion, solvent polarity, post processing is again
It is miscellaneous, the urgent problems to be solved such as extraction times are more, it is extremely limited its application.Catalyst in the present invention, ferrocene
The cuprous cluster of selenium, telluride, has high yield, solvent-free, the reaction time is short etc. breaks through, and will promote the application of C-N coupling synthesis significantly
Prospect.
The content of the invention
It is an object of the invention to provide a kind of cuprous cluster catalyst of ferrocene of catalysis C-N coupling reactions, the catalysis
Agent can optimize reaction condition, improve the application prospect of copper catalysis C-N couplings.
Another object of the present invention also resides in the preparation method for providing above-mentioned catalyst.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of cuprous cluster catalyst of ferrocene of catalysis C-N coupling reactions, the catalyst are used as bound site using Se/Te
Point, and cuprous formation complex, while copper center act synergistically on catalysis, the ferrocene selenium/tellurium with ferrocene center
The cuprous cluster catalyst of ether includes compound, and its structural formula formula is as follows：
[CumXmLa]b
Wherein：
L=；E=Se/Te；N=0 or 1 or 3；a；b；m≥1；X=I or Br；
R=-CH2- orOr
Above-mentioned, the synthesis type of compound is as follows：
Wherein：E=Se/Te；N=0 or 1 or 3；a；b；m≥1；X=I or Br；
R=-CH2- orOr
The structural formula of the part of the above-mentioned cuprous cluster of ferrocene is summarized as follows：
Wherein：E=Se/Te；N=0 or 1 or 3；
R=-CH2- orOr
A series of this cuprous cluster of ferrocene, the activation energy of reaction is greatly reduced, the reaction time is reduced, without molten so as to reach
The reaction condition of agent.Characterize that the catalyst series are catalyzed iodobenzene and imidazoles and react under this condition by gas chromatography one
Serial yield.
Heretofore described selenium/tellurium, Se/Te represent Se or Te.
The invention also discloses the above-mentioned cuprous cluster catalysis of ferrocene selenium/telluride to C-N coupling reactions with catalytic effect
The preparation method of agent, comprises the following steps：
(1) synthesis of ferrocenyl telluride part (by taking L (R=methylene, n=3, E=Te) as an example)：
It is in molar ratio 1 under nitrogen atmosphere：6：1 adds ferrocene, n-BuLi, tellurium in 200-300ml tetrahydrofurans
Powder, after room temperature reaction, reaction solution is spin-dried for, and extracted with dichloromethane.Silica gel column chromatography purifies, and collects Fc2Te2。
Take 100mL three-necked flasks, be in molar ratio 1 under nitrogen atmosphere：8：1 ratio sequentially adds Fc2Te2/
Fc2Se2, sodium borohydride, 1,3- dibromopropanes, at room temperature after reaction completely, vacuum distillation is spin-dried for, and purification obtains yellow solid L.
It will need to only be added in above-mentioned preparation process when preparing similar with above-mentioned ligand structure ferrocenyl selenide part
Tellurium powder changes selenium powder into and can be prepared by ferrocenyl selenide part.
(2) interface method synthesize cuprous cluster (by taking compound L as an example, R=methylene, m=2, a=2, b=1, n=3, X=I,
E=Te)：
The dichloromethane that the ferrocenyl propane selenium/telluride part prepared in step (1) is dissolved in certain volume is weighed, is taken
The amount CuI of material is dissolved in acetonitrile；Acetonitrile solution dropwise is taken after standing a couple of days, to occur to dichloromethane solution upper strata in interface
Cuprous cluster crystal body.
It is catalyzed the experiment of C-N coupling reactions：In single port bottle, iodobenzene 2.5mmol, imidazoles 0.375mmol, tert-butyl alcohol lithium are added
0.5mmol, cuprous cluster catalyst 10%mmol, under nitrogen atmosphere, 110 degrees Celsius, sealing reaction 6 hours；Stoste will be reacted,
Gas-chromatography test is carried out, obtains product 1- phenylimidazole concentration.Yield is obtained after calculating.
The cuprous cluster C-N thermocatalysts property of the ferrocenyl telluride of table one is summarized
The cuprous cluster catalyst C-N thermocatalysts property of the ferrocene selenide of table two is summarized
Beneficial effect：The invention discloses a kind of cuprous cluster catalyst of ferrocene of catalysis C-N coupling reactions, the catalysis
Agent catalytic reaction is rapid, and is reacted under condition of no solvent, can reduce solvent cost and post processing it is cumbersome；The cluster of selection
Compound is stable in the air, and the wide material sources of the catalyst, cheap, itself is non-toxic, environmentally friendly, in catalysis C-
It is widely used in terms of N coupling reactions.
Brief description of the drawings
Fig. 1 is the synthetic route chart of the cuprous cluster catalyst of ferrocene of the present invention.
Embodiment
The present invention is described in detail with reference to embodiment.
Experiment reagent：
Sodium borohydride (CP), cuprous iodide (CP) ferrocene (CP) selenium powder (CP) tellurium powder (CP) are purchased from Chinese medicines group chemistry examination
Agent Co., Ltd；Dichloromethane (AR), ethanol (AR), acetonitrile (AR) are purchased from Wuxi City Ya Sheng Chemical Co., Ltd.s；Anhydrous slufuric acid
Magnesium (AR) is purchased from Shanghai Ling Feng chemical reagent Co., Ltd；Tetrahydrofuran (AR), n-hexane (AR) try four He Weiization purchased from Shanghai
Work Co., Ltd；Silica gel (SILVER REAGENT) is purchased from subsidiary factory of Haiyang Chemical Plant, Qingdao.
Laboratory apparatus：
Rotary Evaporators are purchased from Shanghai Shen Sheng Bioisystech Co., Ltd；Digital display thermostat water bath, magnetic force heating stirrer
Purchased from Guo Hua Electrical Appliances Co., Ltd；Vavuum pump is purchased from Shanghai instrument supply and marketing company；S42-D (III) circulating water types vavuum pump is purchased from Gong
Adopted city Ying Yu Yu Hua instrument plants；Electric vacunm drying case is purchased from Shanghai laboratory apparatus Co., Ltd；Standard Schleck pipelines,
BRUKER DRX500 types NMR, the gas chromatographs of Agilent 789013 are purchased from German Agilent companies, Bruker
SmartApex 2CCD X-rays single crystal diffractometer is purchased from German Bruker companies, the elemental analysers of Perkin Elmer 2400
Purchased from Perkin Elmer companies of the U.S..
Embodiment 1
The preparation (E=Te, n=3) of the cuprous cluster thermocatalyst 1 of ferrocenyl telluride with efficient catalytic C-N couplings：
(1) synthesis (R=methylene, n=3, E=Te) of ferrocenyl telluride ligand L：
Under nitrogen atmosphere, weigh 1mmol ferrocene and be added in 200ml tetrahydrofurans, sequentially add 6mmol normal-butyls
Lithium, 1mmol tellurium powder, after room temperature reaction, reaction solution is spin-dried for, and extracted with dichloromethane.Silica gel column chromatography purifies, and collects
Fc2Te2。
Take 100mL three-necked flasks, under nitrogen atmosphere, the telluride of 0.5mmol ferrocene two dissolved in absolute ethyl alcohol, successively plus
Enter 4mmol sodium borohydrides, 0.5mmol 1,3- dibromopropanes, at room temperature after reaction completely, vacuum distillation is spin-dried for, and purification obtains
Yellow solid L.
(2) interface method synthesizes cuprous cluster 5, (R=methylene, m=2, n=3, a=2, b=1, X=I, E=Te)：
Weigh ligand L and be dissolved in dichloromethane, wait the CuI of the amount of material to be dissolved in acetonitrile.Acetonitrile solution dropwise is to dichloromethane
Solution upper strata.After standing a couple of days, occurs cuprous cluster crystal body at interface.Choose crystal progress X-ray diffraction to test to obtain monocrystalline
Structure.See figure one.
In single port bottle, iodobenzene 2.5mmol, imidazoles 0.375mmol, tert-butyl alcohol lithium 0.5mmol, cuprous cluster catalyst are added
10%mmol, under nitrogen atmosphere, 110 degrees Celsius, sealing reaction 6 hours；Stoste will be reacted, gas-chromatography test is carried out, obtains
Product 1- phenylimidazole concentration.Yield is obtained after calculating.
Embodiment 2
In single port bottle, iodobenzene 2.5mmol, imidazoles 0.375mmol, tert-butyl alcohol lithium 0.5mmol, cuprous iodide 10% are added
Mol, under nitrogen atmosphere, 110 degrees Celsius, sealing reaction 6 hours；Stoste will be reacted, gas-chromatography test is carried out, obtains product 1-
Phenylimidazole concentration.Yield is obtained after calculating.
Embodiment 3
In 10ml single port bottles, iodobenzene 2.5mmol, imidazoles 0.375mmol, tert-butyl alcohol lithium 0.5mmol, (E of catalyst 5 are added
=Te, n=3, m=2, a=2, b=1, X=I) 10%mol, under nitrogen atmosphere, 110 degrees Celsius, sealing reaction 6 hours.Drop
Wen Hou, solid is separated, carry out repeated experiment.In triplicate, third time reaction stoste is subjected to gas phase test, calculates production
Rate.Yield is respectively 99.5%, 91.3%, 89.4%.
The catalytic efficiency summary sheet of three embodiment of table 1,2,3
| Number | 1 | 2 | 3 |
| Catalytic efficiency (%) | 99.9 | Trace | 99.5/91.3/89.4 |
Claims (2)
1. a kind of cuprous cluster catalyst of ferrocene of catalysis C-N coupling reactions, it is characterised in that the catalyst is made with Se/Te
For binding site, and cuprous formation complex, while copper center acts synergistically on catalysis with ferrocene center, described two is luxuriant
Its structural formula is as follows including compound for iron selenium/cuprous cluster catalyst of telluride：
[CumXmLa]b
Wherein：
E=Se/Te；N=0 or 1 or 3；a；b；m≥1；X=I or Br；
R=-CH2- orOr
2. the preparation method of the cuprous cluster catalyst of ferrocene of the catalysis C-N coupling reactions described in claim 1, its feature exist
In the preparation method of the compound comprises the following steps：
(1) synthesis of ferrocenyl selenium/telluride part：
It is in molar ratio 1 under nitrogen atmosphere：6：1 in 200-300ml tetrahydrofurans add ferrocene, n-BuLi, tellurium powder/
Selenium powder, after room temperature reaction, reaction solution is spin-dried for, and extracted with dichloromethane.Silica gel column chromatography purifies, and collects Fc2Te2/Fc2Se2；
It is in molar ratio 1 under nitrogen atmosphere：8：1 ratio sequentially adds Fc2Te2/Fc2Se2, sodium borohydride, 1,3- dibromopropanes
Or a dimethyl bromobenzene or to dimethyl bromobenzene, at room temperature after reaction completely, vacuum distillation is spin-dried for, and purification obtains yellow solid L；
(2) interface method synthesizes cuprous cluster：
Weigh the ferrocenyl propane selenium/telluride ligand L prepared in step (1) and be dissolved in dichloromethane, be 1 according to mol ratio:1 claims
CuI or CuBr is taken to be dissolved in dry acetonitrile, acetonitrile solution is slowly added dropwise to dichloromethane solution upper strata, is occurred in interface cuprous
Cluster crystal body.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997440A (en) * | 2018-07-09 | 2018-12-14 | 浙江工业大学上虞研究院有限公司 | The method that novel ferrocene bidentate ligand, ligand and mantoquita coordination prepare catalyst |
| CN109336934A (en) * | 2018-10-08 | 2019-02-15 | 浙江工业大学上虞研究院有限公司 | Ferrocene bidentate ligand and its application in the asymmetric C-N cross-coupling reaction of copper catalysis |
| CN115108624A (en) * | 2022-07-12 | 2022-09-27 | 南京工业大学 | Ferrocene selenide/TiO 2 Application of quasi-composite photocatalyst in purifying pollutants in water system |
| CN115745007A (en) * | 2022-12-09 | 2023-03-07 | 山西大学 | Preparation method of magnetic carbon nano composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007071792A1 (en) * | 2005-12-23 | 2007-06-28 | Commissariat A L'energie Atomique | Sensitizing complexes, their method of production, hybrid inorganic/ organic semiconductor material comprising them, and photovoltaic cell comprising this material |
| CN104583291A (en) * | 2012-08-29 | 2015-04-29 | 阿克佐诺贝尔化学国际公司 | Iron-based accelerator for curing resins |
| CN104829550A (en) * | 2015-05-04 | 2015-08-12 | 四川大学 | Method for high-efficiency preparation of an o-hydroxyphenyl heterocyclic derivative through C-H/C-H oxidative coupling reaction based on transition metal catalysis |
| CN105944763A (en) * | 2016-05-17 | 2016-09-21 | 南京工业大学 | Cuprous selenide cluster supported visible light photocatalyst with property of reducing Cr (VI) ions |
-
2017
- 2017-11-23 CN CN201711178820.XA patent/CN107803223A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007071792A1 (en) * | 2005-12-23 | 2007-06-28 | Commissariat A L'energie Atomique | Sensitizing complexes, their method of production, hybrid inorganic/ organic semiconductor material comprising them, and photovoltaic cell comprising this material |
| CN104583291A (en) * | 2012-08-29 | 2015-04-29 | 阿克佐诺贝尔化学国际公司 | Iron-based accelerator for curing resins |
| CN104829550A (en) * | 2015-05-04 | 2015-08-12 | 四川大学 | Method for high-efficiency preparation of an o-hydroxyphenyl heterocyclic derivative through C-H/C-H oxidative coupling reaction based on transition metal catalysis |
| CN105944763A (en) * | 2016-05-17 | 2016-09-21 | 南京工业大学 | Cuprous selenide cluster supported visible light photocatalyst with property of reducing Cr (VI) ions |
Non-Patent Citations (5)
| Title |
|---|
| MARK R. BURGESS ET AL.: ""Electrochemical and NMR spectroscopic studies of selenium- and tellurium-substituted ferrocenes II: Diferrocenyl chalcogenides, Fc2E, diferrocenyl dichalcogenides, Fc2E2, and bis(ferrocenylchalcogeno)- alkanes..."", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| WEI JI ET AL.: ""Copper(I) halide clusters based upon ferrocenylchalcogenoether ligands: donors, halides and semi-rigidity effects on the geometry and catalytic activity"", 《DALTON TRANSACTIONS》 * |
| 张龙，贡长生，代斌主编: "《绿色化学》", 31 August 2014 * |
| 李朴等: ""1，1’-二硒取代二茂铁衍生物的合成"", 《高等学校化学学报》 * |
| 王亚楼编著: "《化学制药工艺学》", 31 October 2008 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997440A (en) * | 2018-07-09 | 2018-12-14 | 浙江工业大学上虞研究院有限公司 | The method that novel ferrocene bidentate ligand, ligand and mantoquita coordination prepare catalyst |
| CN109336934A (en) * | 2018-10-08 | 2019-02-15 | 浙江工业大学上虞研究院有限公司 | Ferrocene bidentate ligand and its application in the asymmetric C-N cross-coupling reaction of copper catalysis |
| CN115108624A (en) * | 2022-07-12 | 2022-09-27 | 南京工业大学 | Ferrocene selenide/TiO 2 Application of quasi-composite photocatalyst in purifying pollutants in water system |
| CN115745007A (en) * | 2022-12-09 | 2023-03-07 | 山西大学 | Preparation method of magnetic carbon nano composite material |
| CN115745007B (en) * | 2022-12-09 | 2023-12-26 | 山西大学 | Preparation method of magnetic carbon nanocomposite |
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