CN104447815B - There is triazole-tetrafluoro boric acid copper complex of catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof - Google Patents

There is triazole-tetrafluoro boric acid copper complex of catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof Download PDF

Info

Publication number
CN104447815B
CN104447815B CN201410769386.2A CN201410769386A CN104447815B CN 104447815 B CN104447815 B CN 104447815B CN 201410769386 A CN201410769386 A CN 201410769386A CN 104447815 B CN104447815 B CN 104447815B
Authority
CN
China
Prior art keywords
triazole
tert
copper complex
butylbenzeneboronic
catalysis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201410769386.2A
Other languages
Chinese (zh)
Other versions
CN104447815A (en
Inventor
王英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Normal University
Original Assignee
Tianjin Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin Normal University filed Critical Tianjin Normal University
Priority to CN201410769386.2A priority Critical patent/CN104447815B/en
Publication of CN104447815A publication Critical patent/CN104447815A/en
Application granted granted Critical
Publication of CN104447815B publication Critical patent/CN104447815B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/08—Copper 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • 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
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • 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
    • B01J2531/0238—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
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to triazole-tetrafluoro boric acid copper complex with catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof, disclose one { [Cu (L)] (BF4)2·0.5H2O}(1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) preparation method and as catalysis 4-tert-butylbenzeneboronic acid coupling reaction there is potential using value.It is to use " hydro-thermal method ", i.e. Cu (BF4)2With L 100oC hydrothermal condition gets off to prepare this complex.The present invention further discloses { [Cu (L)] (BF4)2·0.5H2O}(1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) can be as the application in terms of the coupling reaction catalyst of 4-tert-butylbenzeneboronic acid.

Description

There is triazole-tetrafluoro boric acid copper complex and the system thereof of catalysis 4-tert-butylbenzeneboronic acid Preparation Method
The present invention obtains state natural sciences fund general project (21471113), Tianjin Education Commission funded projects (20140506), Tianjin Normal University's Middl-age and youth faculty Academic innovations advances planning item and Tianjin innovation team of institution of higher education Training plan subsidizes (TD12-5038).
Technical field
The invention belongs to Inorganic synthese technical field, relate to copper complex { [Cu (L)] (BF4)2·0.5H2O} (1) (L =4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) preparation method and as 4-tert-butylbenzeneboronic acid Application in terms of the catalyst of coupling reaction.
Background technology
A research always active field of high selectivity is carried out with transition metal complex catalysis.With commonly Synthesizing mean is difficult to the reaction realized, and busy use transition metal complex can a step complete in a mild condition.Therefore, adopt Make catalyst with metal complex and develop the organic synthesis of high selectivity, high conversion, be the most interesting Problem.In organic synthesis, general conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex demonstrates many Sample catalysis.Palladium catalysed cross coupling reaction kind is a lot, and these reactions are at synthesis of natural product, polymer, functional material, liquid Crystalline substance, drug molecule and bioactive compound all have been widely used.But palladium catalyst is relatively costly, if can be with cheap Copper complex replaces expensive palladium catalyst, it is achieved the process of reaction, is possible not only to cost-effective, and is expected to industry metaplasia Produce.
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are that the bridging that coordination ability is stronger is joined Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound the most.These parts can be former with the nitrogen on 1,2 Son forms N1, N2-bridging pattern with metallic ion coordination, can be by 2,4 for 4 unsubstituted 1,2,4-triazole derivatives On nitrogen-atoms formed N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, N3-bridging pattern Similar.Specific use for triazole class compounds is also manifested by the design of molecular device, and synthesis has different dimension Metal complex has been the vital step of device.
The present invention is i.e. to select Cu (BF4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100oC hydrothermal condition gets off to prepare copper complex { [Cu (L)] (BF4)2·0.5H2O} (1).Catalysis experiments proves, should Complex can be applied as the catalyst of 4-tert-butylbenzeneboronic acid coupling reaction.
Summary of the invention
Offer double triazole copper complex { [Cu (L)] (BF of a kind of isophthalic is provided4)2· 0.5H2O} (1) monocrystalline and preparation method thereof.
Following technical scheme is current inventor provides for this:
Double triazole copper complex { [Cu (L)] (BF of isophthalic4)2·0.5H2O} (1) (L=4-(3-(4H-1,2,4-tri- Azoles-4-base) phenyl)-4H-1,2,4-triazole) and structural motif as shown in Figure 1.
The present invention further discloses double triazole copper complex { [Cu (L)] (BF of isophthalic4)2·0.5H2O} (1) (L = 4-(3-(4H-1,2,4-triazole-4-yls) phenyl)-4H-1,2,4-triazoles) monocrystalline, it is characterised in that this mono-crystalline structures uses APEX II CCD single crystal diffractometer, use is incident radiation through graphite monochromatised Mok alpha ray (λ=0.71073), Collect point diffraction with ω-2 θ scan mode, obtain cell parameter through least square refinement, from difference Fourier electron density Desire to make money or profit and solve single crystal data with software:
The crystallographic data of table 1. complex 1
Double triazole copper complex { [Cu (L)] (BF of isophthalic of the present invention4)2·0.5H2O} (1) (L = 4-(3-(4H- 1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazoles) preparation method of monocrystalline, its feature is using " hydro-thermal method ", CH3CN and H2In O, by Cu (BF4)2With L ligand 1 00oReact under C hydrothermal condition, obtain being suitable for the yellow of X-ray single crystal diffraction Rhabdolith.Wherein CH3CN and H2The volume ratio of O is 4:6, Cu (BF4)2It is 1:1 with the mol ratio of L；
The more detailed preparation method of the present invention is as follows:
Double triazole copper complex { [Cu (L)] (BF of a kind of isophthalic4)2·0.5H2O} (1) (L = 4-(3-(4H-1,2,4- Triazole-4-yl) phenyl)-4H-1,2,4-triazoles) preparation method of monocrystalline, its feature is using " hydro-thermal method ", at CH3CN and H2O In, by Cu (BF4)2With L ligand 1 00oReact under C hydrothermal condition, obtain being suitable for the yellow rhabdolith of X-ray single crystal diffraction. Wherein CH3CN and H2The volume ratio of O is 4:6, Cu (BF4)2It is 1:1 with the mol ratio of L；
Solvent of the present invention is mixed solvent, CH3CN and H2O。
Wherein Cu (BF4)2It is 1:1 with the mol ratio of L.
The present invention further discloses the double triazole copper complex of a kind of isophthalic, to have catalysis 4-tert-butylbenzeneboronic acid coupling anti- The effect answered.
Double triazole copper complex { [Cu (L)] (BF of a kind of isophthalic disclosed by the invention4)2·0.5H2O} (1) (L = 4- (3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline have the advantage that and feature be:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) { [Cu (L)] (BF prepared by the present invention4)2·0.5H2O} (1) (L=4-(3-(4H-1,2,4-tri- Azoles-4-base) phenyl)-4H-1,2,4-triazoles) production cost is low, and method is easy, is suitable for large-scale production.
Accompanying drawing explanation
The crystal structure primitive figure of Fig. 1: complex 1；
The tomograph of Fig. 2: complex 1.
The nuclear-magnetism figure of Fig. 3: 4,4'-di-t-butyl biphenyl.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, and embodiment is only explanatory, is in no way intended to it Limit the scope of the present invention by any way.All of raw material is all to buy from chemical reagents corporation both domestic and external, does not has Through continuation purification but directly use.Wherein Cu (BF4)2, CH3CN is by commercially available.
Embodiment 1
The preparation of 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) part
It is separately added into m-phenylene diamine (MPD) (1 in equipped with 50 mL three neck round bottom flasks of magneton, reflux condenser and thermometer Mmol), double formylhydrazines (2 mmol), start and stir at 100 DEG C, react 12 hours.After reaction terminates, reactant liquor is down to room Temperature, separates out a large amount of precipitation, by precipitation water and ethyl alcohol recrystallization, yield 86%.Elementary analysis C10H8N6Theoretical value: C, 56.60； H, 3.80；N, 39.60.Experiment value: C, 56.56；H, 3.75；N, 39.56.M-phenylene diamine (MPD), the mol ratio of double formylhydrazines is 1:2.
Embodiment 2
Cu(BF4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) mol ratio of (L) is 1:1；
L (0.0424 g, 0.2 mmol), Cu (BF4)2(0.0691 g, 0.2 mmol), H2O (6 mL), CH3CN (4 mL), hydro-thermal 100oC was slowly dropped to room temperature after tri-days.The yellow having applicable X-ray single crystal diffraction to analyze after driving still is bar-shaped Crystal.Productivity: 35% (calculating based on L).Elementary analysis (C10H9BCuF4N6O0.5) theoretical value (%): C, 32.32；H, 2.44；N, 22.62.Measured value: C, 32.35；H, 2.46；N, 22.69.
Embodiment 2
Crystal structure determination uses APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha ray (λ= 0.71073) it is incident radiation, collects point diffraction with ω-2 θ scan mode, obtain structure cell ginseng through least square refinement Number, utilizes software to solve crystal structure from difference Fourier electron-density map, and through Lorentz lorentz and polarity effect correction.All of H atom is synthesized by difference Fourier and determines through preferable position calculation.Detailed axonometry data are shown in Table 1.Structural motif is shown in Fig. 1, the three-dimensional structure of complex is shown in Fig. 2.
The crystallographic data of table 1. complex 1
Embodiment 3
Cu(BF4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) mol ratio of (L) is 1: 1；
We also attempted other ratios, such as Cu (BF4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H- 1,2,4-triazole) mol ratio be 2:1, the most no matter the length of hydro-thermal reaction time, all can not get crystalline compound.Therefore Cu (BF4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) mol ratio be 1:1 be that optimum response is joined Ratio.
Embodiment 4
A research always active field of high selectivity is carried out with transition metal complex catalysis.With commonly Synthesizing mean is difficult to the reaction realized, and busy use transition metal complex can a step complete in a mild condition.Therefore, adopt Make catalyst with metal complex and develop the organic synthesis of high selectivity, high conversion, be the most interesting Problem.In organic synthesis, general conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex demonstrates many Sample catalysis.Palladium catalysed cross coupling reaction kind is a lot, and these reactions are at synthesis of natural product, polymer, functional material, liquid Crystalline substance, drug molecule and bioactive compound all have been widely used.But palladium catalyst is relatively costly, if can be with cheap Copper complex replaces expensive palladium catalyst, it is achieved the process of reaction, is possible not only to cost-effective, and is expected to industry metaplasia Produce.
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are that the bridging that coordination ability is stronger is joined Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound the most.These parts can be former with the nitrogen on 1,2 Son forms N1, N2-bridging pattern with metallic ion coordination, can be by 2,4 for 4 unsubstituted 1,2,4-triazole derivatives On nitrogen-atoms formed N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, N3-bridging pattern Similar.Specific use for triazole class compounds is also manifested by the design of molecular device, and synthesis has different dimension Metal complex has been the vital step of device.
The present invention is i.e. to select Cu (BF4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100oC hydrothermal condition gets off to prepare copper complex { [Cu (L)] (BF4)2·0.5H2O} (1).Catalysis experiments proves, should Complex can be applied as the catalyst of 4-tert-butylbenzeneboronic acid coupling reaction.
1 g 4-tert-butylbenzeneboronic acid, 0.2 g Cs is weighed in 25 mL beakers2CO3, 3 mL DMF and 0.1 g catalyst (complex 1), stirs 1 hour under room temperature, and TLC monitoring (PE:EA=1:1) reaction is complete, 10 mL CH2Cl2After extracted products Again with 20 mL distilled water washings, organic phase sewage MgSO4Being dried, filter, precipitation, the thick product obtained elutes with petroleum ether Cross post, obtain 4,4'-di-t-butyl biphenyl.

Claims (2)

1. the double triazole copper complex monocrystalline of isophthalic is as the application in terms of 4-tert-butylbenzeneboronic acid coupling reaction catalyst, its feature It is that this mono-crystalline structures uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, λ= 0.71073 is incident radiation, collects point diffraction with ω-2 θ scan mode, obtains cell parameter through least square refinement, Software is utilized to solve single crystal data from difference Fourier electron-density map:
The molecular formula of the double triazole copper complex monocrystalline of described isophthalic: [Cu (L)] (BF4)2·0.5H2O, wherein L=4-(3- (4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole.
Application the most according to claim 1, wherein the method for 4-tert-butylbenzeneboronic acid coupling reaction is as follows:
1 g 4-tert-butylbenzeneboronic acid, 0.2 g Cs is weighed in 25 mL beakers2CO3, the catalyst of 3 mL DMF and 0.1 g is joined Compound monocrystalline, stirs 1 hour under room temperature, and TLC monitors, 10 mL CH2Cl2Again with 20 mL distilled water washings after extracted products, have Anhydrous MgSO used mutually by machine4Being dried, filter, precipitation, the thick product obtained strips post with petroleum ether, obtains 4,4'-di-t-butyl Biphenyl.
CN201410769386.2A 2014-12-15 2014-12-15 There is triazole-tetrafluoro boric acid copper complex of catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof Expired - Fee Related CN104447815B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410769386.2A CN104447815B (en) 2014-12-15 2014-12-15 There is triazole-tetrafluoro boric acid copper complex of catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410769386.2A CN104447815B (en) 2014-12-15 2014-12-15 There is triazole-tetrafluoro boric acid copper complex of catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104447815A CN104447815A (en) 2015-03-25
CN104447815B true CN104447815B (en) 2016-07-06

Family

ID=52894629

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410769386.2A Expired - Fee Related CN104447815B (en) 2014-12-15 2014-12-15 There is triazole-tetrafluoro boric acid copper complex of catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104447815B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104402912A (en) * 2014-11-10 2015-03-11 天津师范大学 Triazole Cu-boric acid complex with potential ferroelectric function and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104402912A (en) * 2014-11-10 2015-03-11 天津师范大学 Triazole Cu-boric acid complex with potential ferroelectric function and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal–organic frameworks;Kasi Pitchumani et al.;《Green Chemistry》;20140224;第16卷;第2865-2875页 *
Clay encapsulated Cu(OH)xpromoted homocoupling of arylboronic acids: An efficient and eco-friendly protocol;Baldev Singh et al.;《Applied Catalysis A:General》;20131108;第470卷;第232-238页 *
Homocoupling of Arylboronic Acids Catalyzed by 1,10-Phenanthroline-Ligated Copper Complexes in Air;N Kirai et al.;《Eur. J. Org. Chem.》;20091231;第12卷;第1864-1867页 *
Synthesis，Crystal Structure，and Properties of a 3D Cu(I) Coordination Polymer Based on Cu3(CN)2 Clusters and 1,3-Di-(1,2,4-Triazole-4-yl)Benzene;Shao-Bin Miao et al.;《J Clust Sci.》;20140202;第25卷;第1137-1145页 *

Also Published As

Publication number Publication date
CN104447815A (en) 2015-03-25

Similar Documents

Publication Publication Date Title
CN104497018B (en) Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex
CN104557980B (en) Triazole-copper triflate coordination compound with catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof
CN104402913B (en) Double triazole-cupric perchlorate coordination compound of anthracene nucleus with catalysis phenylboric acid and preparation method thereof
CN104557986B (en) Have and be catalyzed triazole-copper triflate coordination compound to fluorobenzoic boric acid and preparation method thereof
CN104447816B (en) There is catalysis triazole-Tetrafluoroboric acid copper complex to fluorobenzoic boric acid and preparation method thereof
CN104530097B (en) Double triazole-tetrafluoro boric acid copper complex of anthracene nucleus with catalysis phenyl boric acid and preparation method thereof
CN104447815B (en) There is triazole-tetrafluoro boric acid copper complex of catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof
CN104447814B (en) Double triazole-tetrafluoro boric acid copper complex of anthracene nucleus with catalysis 4-methoxyphenylboronic acid and preparation method thereof
CN104557985B (en) Oxygen ether dual-triazole copper complex capable of catalyzing p-fluorophenylboronic acid and preparation method of oxygen ether dual-triazole copper complex
CN104497025B (en) Have and be catalyzed double triazole-Tetrafluoroboric acid copper complex of the anthracene nucleus to methylphenylboronic acid and preparation method thereof
CN104497024B (en) There is triazole-cupric perchlorate complex of catalysis 3-methoxyphenylboronic acid and preparation method thereof
CN104497021B (en) There is triazole-Tetrafluoroboric acid copper complex of catalysis 4-methoxyphenylboronic acid and preparation method thereof
CN104447812B (en) Have and be catalyzed triazole-cupric perchlorate coordination compound to methylphenylboronic acid and preparation method thereof
CN104497020B (en) There is triazole-cupric perchlorate coordination compound of catalysis 4-pyridine phenylboric acid and preparation method thereof
CN104513260B (en) There is triazole-copper triflate coordination compound of catalysis 4-methoxyphenylboronic acid and preparation method thereof
CN104530093B (en) Triazole-copper tetrafluoroborate complex for catalyzing 4-methoxyphenylboronic acid and preparation method thereof
CN104530094B (en) Triazole-cupric perchlorate coordination compound with catalysis 4-methoxyphenylboronic acid and preparation method thereof
CN104478906B (en) Double triazole copper complex of anthracene nucleus with catalysis 3-methoxyphenylboronic acid and preparation method thereof
CN104557984B (en) Triazole-copper trifluoromethanesulfonate complex capable of catalyzing phenylboronic acid and preparation method of triazole-copper trifluoromethanesulfonate complex
CN104860965B (en) Triazole-copper triflate coordination compound with catalysis 4-pyridine phenylboric acid and preparation method thereof
CN104557982B (en) Triazole-copper triflate complex with effect of catalyzing p-Tolylboronic acid and preparation method thereof
CN104447808B (en) Triazole-cupric perchlorate coordination compound with catalysis phenylboric acid and preparation method thereof
CN104530095B (en) Double triazole-cupric perchlorate coordination compound of anthracene nucleus with catalysis 3-methoxyphenylboronic acid and preparation method thereof
CN104478901B (en) Double triazole-cupric perchlorate coordination compound of anthracene nucleus with catalysis phenylboric acid and preparation method thereof
CN104497019B (en) Double triazole-cupric perchlorate complex of anthracene nucleus with catalysis 4-methoxyphenylboronic acid and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160706

Termination date: 20161215

CF01 Termination of patent right due to non-payment of annual fee