CN104557980A - Triazole-copper trifluoromethanesulfonate complex capable of catalyzing 4-tert-butylphenylboronic acid and preparation method of triazole-copper trifluoromethanesulfonate complex - Google Patents

Triazole-copper trifluoromethanesulfonate complex capable of catalyzing 4-tert-butylphenylboronic acid and preparation method of triazole-copper trifluoromethanesulfonate complex Download PDF

Info

Publication number
CN104557980A
CN104557980A CN201410767870.1A CN201410767870A CN104557980A CN 104557980 A CN104557980 A CN 104557980A CN 201410767870 A CN201410767870 A CN 201410767870A CN 104557980 A CN104557980 A CN 104557980A
Authority
CN
China
Prior art keywords
triazole
phenyl
complex
tert
copper complex
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.)
Granted
Application number
CN201410767870.1A
Other languages
Chinese (zh)
Other versions
CN104557980B (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 CN201410767870.1A priority Critical patent/CN104557980B/en
Publication of CN104557980A publication Critical patent/CN104557980A/en
Application granted granted Critical
Publication of CN104557980B publication Critical patent/CN104557980B/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
    • B01J31/22—Organic complexes
    • 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
    • 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

Abstract

The invention discloses a triazole-copper trifluoromethanesulfonate complex capable of catalyzing 4-tert-butylphenylboronic acid and a preparation method of the triazole-copper trifluoromethanesulfonate complex. The complex is prepared from Cu(CF3SO3)2 and L by adopting a 'hydrothermal method' under the hydrothermal condition of 100 DEG C. The invention further discloses application of the copper complex ((Cu(L))(CF3SO3).0.33H2O) (1) (L=4-(3-(4H-1, 2, 4-triazole-4-yl) phenyl)-4H-1, 2, 4-trizole) as a coupling reaction catalyst of 4-tert-butylphenylboronic acid.

Description

Triazole-copper triflate complex with catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof
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 to subsidize (TD12-5038).
Technical field
The invention belongs to Inorganic synthese technical field, relate to copper complex { [Cu (L)] (CF 3sO 3) 0.33H 2o} ( 1) application of the preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) and the catalyst aspect as 4-tert-butylbenzeneboronic acid coupling reaction.
Background technology
The research carrying out high selectivity with transition metal complex catalysis is an active field always.Be difficult to the reaction realized with common synthesizing mean, busy use transition metal complex can a step complete in a mild condition.Therefore, adopting metal complex to make catalyst to develop the organic synthesis of high selectivity, high conversion, is very interesting problem.In organic synthesis, general conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex demonstrates diversity catalysis.Palladium catalysed cross coupling reaction kind is a lot, and these reactions all have been widely used in synthesis of natural product, polymer, functional material, liquid crystal, drug molecule and bioactive compound.But palladium catalyst is relatively costly, if can replace expensive palladium catalyst with cheap copper complex, the process of realization response, not only can be cost-saving, and be expected to suitability for industrialized production.
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridging ligands that coordination ability is stronger, have synthesized at present and have characterized a large amount of monokaryons, multinuclear and multidimensional compound.These parts can with 1, nitrogen-atoms on 2 and metallic ion coordination form N1, N2-bridging pattern, for 4 unsubstituted 1,2,4-triazole derivative is by 2, nitrogen-atoms on 4 forms N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, and N3-bridging Pattern Class seemingly.Specific use for triazole class compounds also shows in the design of molecular device, and the metal complex that synthesis has different dimension has been the vital step of device.
The present invention selects Cu (CF 3sO 3) 2with 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100 oc hydrothermal condition gets off to prepare copper complex { [Cu (L)] (CF 3sO 3) 0.33H 2o} ( 1).Catalysis experiments proves, the catalyst that this complex can be used as 4-tert-butylbenzeneboronic acid coupling reaction is applied.
Summary of the invention
Another object of the present invention is to provide a kind of isophthalic two triazole copper complex { [Cu (L)] (CF 3sO 3) 0.33H 2o} ( 1) monocrystalline and preparation method thereof.
Current inventor provides following technical scheme for this reason:
Two triazole copper complex { [Cu (L)] (CF of isophthalic 3sO 3) 0.33H 2o} ( 1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) structural motif as shown in Figure 1.
The present invention further discloses two triazole copper complex { [Cu (L)] (CF of isophthalic 3sO 3) 0.33H 2o} ( 1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline, it is characterized in that this mono-crystalline structures adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains cell parameter, utilize software to solve single crystal data from difference Fourier electron-density map through least square refinement:
Table 1. complex 1crystallographic data
Two triazole copper complex { [Cu (L)] (CF of isophthalic of the present invention 3sO 3) 0.33H 2o} ( 1) preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline, its feature in employing " hydro-thermal method ", at CH 3cN and H 2in O, by Cu (CF 3sO 3) 2with L ligand 1 00 oreact under C hydrothermal condition, obtain the yellow rhabdolith of applicable X-ray single crystal diffraction.Wherein CH 3cN and H 2the volume ratio of O is 4:6, Cu (CF 3sO 3) 2be 1:1 with the mol ratio of L;
The more detailed preparation method of the present invention is as follows:
Two triazole copper complex { [Cu (L)] (CF of a kind of isophthalic 3sO 3) 0.33H 2o} ( 1) preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline, its feature in employing " hydro-thermal method ", at CH 3cN and H 2in O, by Cu (CF 3sO 3) 2with L ligand 1 00 oreact under C hydrothermal condition, obtain the yellow rhabdolith of applicable X-ray single crystal diffraction.Wherein CH 3cN and H 2the volume ratio of O is 4:6, Cu (CF 3sO 3) 2be 1:1 with the mol ratio of L;
Solvent of the present invention is mixed solvent, CH 3cN and H 2o.Wherein Cu (CF 3sO 3) 2be 1:1 with the mol ratio of L.
The present invention further discloses copper complex { [Cu (L)] (CF 3sO 3) 0.33H 2o} ( 1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) can be used as the catalyst of 4-tert-butylbenzeneboronic acid coupling reaction.
Two triazole copper complex { [Cu (L)] (CF of a kind of isophthalic disclosed by the invention 3sO 3) 0.33H 2o} ( 1) advantage and disadvantage that has of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline is:
(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)] (CF prepared by the present invention 3sO 3) 0.33H 2o} ( 1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) production cost is low, method is easy, is applicable to large-scale production.
Accompanying drawing explanation
Fig. 1: complex 1crystal structure primitive figure;
Fig. 2: complex 1tomograph.
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 indicative, never means that it limits the scope of the invention by any way.All raw materials are all buy from chemical reagents corporation both domestic and external, such as phenylenediamine, two formylhydrazine.Through continuation purify but directly use.
Embodiment 1
The preparation of 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) part
In 50 mL, tri-mouthfuls of round-bottomed flasks that magneton, reflux condenser and thermometer are housed, add m-phenylene diamine (MPD) (1 mmol) respectively, two formylhydrazine (2 mmol), starts and is stirred in 100 DEG C, reacts 12 hours.After reaction terminates, reactant liquor is down to room temperature, separates out and precipitate in a large number, by precipitation water and ethyl alcohol recrystallization, yield 86%.Elementary analysis C 10h 8n 6theoretical 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 two formylhydrazine is 1:2.
Embodiment 2
Cu (CF 3sO 3) 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 (CF 3sO 3) 2(0.0691 g, 0.2 mmol), H 2o (6 mL), CH 3cN (4 mL), hydro-thermal 100 oc is slowly down to room temperature in tri-days afterwards.The yellow rhabdolith that applicable X-ray single crystal diffraction is analyzed is had after driving still.Productive rate: 35% (calculating based on L).Elementary analysis (C 33h 26cu 3f 9n 18o 10s 3) theoretical value (%): C, 30.67; H, 2.03; N, 19.51.Measured value: C, 30.69; H, 2.06; N, 19.59.
We also attempted other ratios, such as Cu (CF 3sO 3) 2be 2:1 with the mol ratio of L, then the length of no matter hydro-thermal reaction time, all can not get crystalline compound.Therefore Cu (CF 3sO 3) 2be 1:1 with the mol ratio of L be optimum response proportioning.
Embodiment 3
Crystal structure determination adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains cell parameter, utilize software to solve crystal structure from difference Fourier electron-density map through least square refinement, and through Lorentz lorentz and polarity effect correction.All H atom are synthesized by difference Fourier and are determined through desirable position calculation.Detailed axonometry data are in table 1.Structural motif is shown in Fig. 1, and the three-dimensional structure of complex is shown in Fig. 2.
Table 1. complex 1crystallographic data
Embodiment 4
The research carrying out high selectivity with transition metal complex catalysis is an active field always.Be difficult to the reaction realized with common synthesizing mean, busy use transition metal complex can a step complete in a mild condition.Therefore, adopting metal complex to make catalyst to develop the organic synthesis of high selectivity, high conversion, is very interesting problem.In organic synthesis, general conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex demonstrates diversity catalysis.Palladium catalysed cross coupling reaction kind is a lot, and these reactions all have been widely used in synthesis of natural product, polymer, functional material, liquid crystal, drug molecule and bioactive compound.But palladium catalyst is relatively costly, if can replace expensive palladium catalyst with cheap copper complex, the process of realization response, not only can be cost-saving, and be expected to suitability for industrialized production.
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridging ligands that coordination ability is stronger, have synthesized at present and have characterized a large amount of monokaryons, multinuclear and multidimensional compound.These parts can with 1, nitrogen-atoms on 2 and metallic ion coordination form N1, N2-bridging pattern, for 4 unsubstituted 1,2,4-triazole derivative is by 2, nitrogen-atoms on 4 forms N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, and N3-bridging Pattern Class seemingly.Specific use for triazole class compounds also shows in the design of molecular device, and the metal complex that synthesis has different dimension has been the vital step of device.
The present invention selects Cu (CF 3sO 3) 2with 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100 oc hydrothermal condition gets off to prepare copper complex { [Cu (L)] (CF 3sO 3) 0.33H 2o} ( 1).Catalysis experiments proves, the catalyst that this complex can be used as 4-tert-butylbenzeneboronic acid coupling reaction is applied.
    
1 g 4-tert-butylbenzeneboronic acid is taken, 0.2 g Cs in 25 mL beakers 2cO 3, 3 mL DMF and 0.1 g catalyst (complex 1), stirred at ambient temperature 1 hour, TLC monitoring (PE:EA=1:1) reacts completely, 10 mL CH 2cl 2again with 20 mL distilled water washings after extracted products, organic phase sewage MgSO 4drying, filter, precipitation, the thick product obtained strips post with benzinum, obtains 4,4'-di-t-butyl biphenyl.

Claims (4)

1. two triazole copper complex { [Cu (L)] (CF of isophthalic 3sO 3) 0.33H 2o} ( 1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) structural motif as shown in drawings.
2. the monocrystalline of copper complex described in claim 1, is characterized in that this mono-crystalline structures adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains cell parameter, utilize software to solve single crystal data from difference Fourier electron-density map through least square refinement:
Table 1. complex 1crystallographic data
。
3. { [Cu (L)] (CF of copper complex described in claim 1 3sO 3) 0.33H 2o} ( 1) preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole), it is characterized in that adopting it to be adopt " hydro-thermal method ", i.e. Cu (CF 3sO 3) 2with 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100 oc hydrothermal condition gets off and prepares this complex;
Described solvent is mixed solvent is CH 3cN and H 2o;
Wherein Cu (CF 3sO 3) 2be 1:1 with the mol ratio of 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L).
4. { [Cu (L)] (CF of copper complex described in claim 1 3sO 3) 0.33H 2o} ( 1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) can be used as the application of the coupling reaction catalyst aspect of 4-tert-butylbenzeneboronic acid.
CN201410767870.1A 2014-12-15 2014-12-15 Triazole-copper triflate coordination compound with catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof Expired - Fee Related CN104557980B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410767870.1A CN104557980B (en) 2014-12-15 2014-12-15 Triazole-copper triflate coordination compound with catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410767870.1A CN104557980B (en) 2014-12-15 2014-12-15 Triazole-copper triflate coordination compound with catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104557980A true CN104557980A (en) 2015-04-29
CN104557980B CN104557980B (en) 2016-06-08

Family

ID=53075142

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410767870.1A Expired - Fee Related CN104557980B (en) 2014-12-15 2014-12-15 Triazole-copper triflate coordination compound with catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104557980B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105837603A (en) * 2016-04-25 2016-08-10 天津师范大学 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylbiphenyldicarboxylic acid copper complex monocrystal and application thereof
CN105837605A (en) * 2016-04-25 2016-08-10 天津师范大学 1, 4-dimethyl-2, 5-bi-1H-1, 2, 4-bis (triazol 1 yl) two-dimensional copper complex single crystal and application

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104447804A (en) * 2014-11-10 2015-03-25 天津师范大学 M-benzene bitriazole Cu-trifluoromethanesulfonic acid complex as well as preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104447804A (en) * 2014-11-10 2015-03-25 天津师范大学 M-benzene bitriazole Cu-trifluoromethanesulfonic acid complex as well as preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BALDEV SINGH ET AL.: "Clay encapsulated Cu(OH)xpromoted homocoupling of arylboronic acids: An efficient and eco-friendly protocol", 《APPLIED CATALYSIS A:GENERAL》 *
KASI PITCHUMANI ET AL.: "Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal–organic frameworks", 《GREEN CHEMISTRY》 *
N KIRAI ET AL.: "Homocoupling of Arylboronic Acids Catalyzed by 1,10-Phenanthroline-Ligated Copper Complexes in Air", 《EUR. J. ORG. CHEM.》 *
SHAO-BIN MIAO ET AL.: "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", 《J CLUST SCI.》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105837603A (en) * 2016-04-25 2016-08-10 天津师范大学 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylbiphenyldicarboxylic acid copper complex monocrystal and application thereof
CN105837605A (en) * 2016-04-25 2016-08-10 天津师范大学 1, 4-dimethyl-2, 5-bi-1H-1, 2, 4-bis (triazol 1 yl) two-dimensional copper complex single crystal and application

Also Published As

Publication number Publication date
CN104557980B (en) 2016-06-08

Similar Documents

Publication Publication Date Title
CN104497018A (en) Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex
CN104513261A (en) Oxylether bistriazole for catalysis of 4-tert-butylphenylboronic acid and preparation method thereof
CN104557980A (en) Triazole-copper trifluoromethanesulfonate complex capable of catalyzing 4-tert-butylphenylboronic acid and preparation method of triazole-copper trifluoromethanesulfonate complex
CN104447809A (en) Anthracene ring bitriazole-cupric tetrafluoroborate complex capable of catalyzing p-fluorophenylboronic acid and preparation method of complex
CN104402913A (en) Anthracene-ring bis (triazol 1 yl) copper perchlorate complex with catalyst phenylboronic acid and preparation method thereof
CN104557986A (en) Triazole-copper trifluoromethane sulfonate complex capable of catalyzing p-fluoro-phenyl boric acid and preparation method of triazole-copper trifluoromethane sulfonate complex
CN104447816A (en) Triazole and copper fluoroborate complex with p-fluorophenylboronic acid catalysis effect and preparation method of triazole and copper fluoroborate complex
CN104447810B (en) Triazole-copper triflate title complex with catalysis 3-methoxyphenylboronic acid and preparation method thereof
CN104557984A (en) Triazole-copper trifluoromethanesulfonate complex capable of catalyzing phenylboronic acid and preparation method of triazole-copper trifluoromethanesulfonate complex
CN104557985A (en) Oxygen ether dual-triazole copper complex capable of catalyzing p-fluorophenylboronic acid and preparation method of oxygen ether dual-triazole copper complex
CN104497024B (en) There is triazole-cupric perchlorate complex of catalysis 3-methoxyphenylboronic acid and preparation method thereof
CN104557982A (en) Triazole-copper triflate complex with effect of catalyzing p-Tolylboronic acid and preparation method thereof
CN104497022B (en) Triazole-cupric perchlorate title complex with catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof
CN104530097A (en) Anthracycline bis-triazole-copper tetrafluoroborate complex for catalyzing phenylboronic acid and preparation method thereof
CN104447807B (en) Triazole-Tetrafluoroboric acid copper complex with catalysis phenylo boric acid and preparation method thereof
CN104478903A (en) Anthracene-ring bitriazol-cupric tetrafluoroborate complex capable of catalyzing 3-methoxy phenylboronic acid and preparation method thereof
CN104478904A (en) Anthracene-ring bitriazol-cupric tetrafluoroborate complex capable of catalyzing 4-tert-butyl phenylboronic acid and preparation method thereof
CN104478902B (en) Triazole-Tetrafluoroboric acid copper complex with catalysis 3-methoxyphenylboronic 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
CN104447814A (en) Anthracycline bitriazole and copper fluoroborate complex with 4-methoxyphenylboronic acid catalysis effect and preparation method of anthracycline bitriazole and copper fluoroborate complex
CN104497020B (en) There is triazole-cupric perchlorate coordination compound of catalysis 4-pyridine phenylboric acid and preparation method thereof
CN104530096B (en) Triazole-Tetrafluoroboric acid copper complex with catalysis 4-pyridine phenylo boric acid and preparation method thereof
CN104497025A (en) Anthracycline bitriazole and copper fluoroborate complex with 4-methylbenzeneboronic acid catalyzing effect and preparation method of anthracycline bitriazole and copper fluoroborate complex
CN104513260A (en) Triazole-trifluoromethane sulfonic acid copper complex for catalysis of 4-methoxyphenylboronic acid and preparation method thereof
CN104860965A (en) Triazole-copper(II) trifluoromethanesulfonate complex for catalysis of 4-pyridine phenylboronic acid and preparation method therefor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160608

Termination date: 20161215