CN105837603A - 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylbiphenyldicarboxylic acid copper complex monocrystal and application thereof - Google Patents
1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylbiphenyldicarboxylic acid copper complex monocrystal and application thereof Download PDFInfo
- Publication number
- CN105837603A CN105837603A CN201610255172.2A CN201610255172A CN105837603A CN 105837603 A CN105837603 A CN 105837603A CN 201610255172 A CN201610255172 A CN 201610255172A CN 105837603 A CN105837603 A CN 105837603A
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- bpdca
- dicarboxylic acid
- copper complex
- triazole
- 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.)
- Pending
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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation 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
- B01J2531/02—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
Abstract
The invention discloses a 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylbiphenyldicarboxylic acid copper complex monocrystal, and a preparation method and application thereof. The structure is [Cu(L)(H2O)(bpdca)], wherein L is 1-(2,5-dimethyl-4-(1H-1,2,4-triazolyl-1-yl)phenyl)-1H-1,2,4-triazole; and bpdca is biphenyldicarboxylic acid. The invention also discloses a preparation method of the monocrystal. The method adopts a normal-temperature volatilization process, and comprises the following steps: stirring L, bpdca and Cu(NO3)2.6H2O in a water for half an hour, filtering, and volatilizing the filtrate at normal temperature for two weeks, thereby obtaining the blue massive crystal suitable for X-ray single-crystal diffraction, wherein the L:bpdca:Cu(NO3)2.6H2O mole ratio is 1:1:1. The invention also discloses application of the 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylbiphenyldicarboxylic acid copper complex monocrystal specially as a catalyst for generating 4,4'-difluorobiphenyl from p-fluorophenyl boric acid.
Description
The present invention obtains the subsidy of Tianjin innovation team of Education Commission (TD12-5037).
Technical field
The invention belongs to organic and Inorganic synthese technical field, relate to Isosorbide-5-Nitrae-dimethyl-2, the double triazole biphenyl of 5-bis--1H-
Dioctyl phthalate copper complex monocrystalline [Cu (L) (H2O) (bpdca)] preparation method and as the application in terms of catalyst, wherein, L
=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；Bpdca=biphenyl dicarboxylic acid.
Background technology
1,2,4-triazole and derivant 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 use room temperature volatility process, i.e. L, bpdca and Cu (NO3)2·6H2O stirs mistake after half an hour in water
Filter, filtrate room temperature obtains being suitable for the blue bulk crystals of X-ray single crystal diffraction after volatilizing two weeks, structure is [Cu (L) (H2O)
(bpdca)], wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yls) phenyl)-1H-1,2,4-triazoles；
Bpdca=biphenyl dicarboxylic acid.This coordination compound is alternatively arranged as generating fluorobenzoic boric acid the catalyst of 4,4'-DfBP and is answered
With.
Summary of the invention
Following technical scheme is current inventor provides for this:
A kind of Isosorbide-5-Nitrae-dimethyl-2, the monocrystalline of the double triazole biphenyl dicarboxylic acid copper complex of 5-bis--1H-, it is characterised in that this monocrystalline
Structure uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, and λ=0.71073 is for entering
Penetrate radiation, collect point diffraction with ω-2 θ scan mode, obtain cell parameter through least square refinement, from difference Fourier
Electron density map utilizes software to solve single crystal data:
Its structure is as follows:
[Cu(L)(H2O) (bpdca)], wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Bpdca=biphenyl dicarboxylic acid.
The present invention further discloses the double triazole biphenyl dicarboxylic acid copper complex monocrystalline of 1,4-dimethyl-2,5-two-1H-
Preparation method, it is characterised in that it is to use room temperature volatility process, by L, bpdca and Cu (NO3)2·6H2It is little that O stirs half in water
Filtering time after, filtrate room temperature obtains being suitable for the blue bulk crystals of X-ray single crystal diffraction after volatilizing two weeks；Wherein L:bpdca:
Cu(NO3)2·6H2The mol ratio of O is 1:1:1；
The structure of the double triazole biphenyl dicarboxylic acid copper complex monocrystalline of 1,4-dimethyl-2,5-two-1H-is [Cu (L) (H2O)
(bpdca)]；Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Bpdca=biphenyl dicarboxylic acid；
L bpdca。
The present invention further discloses the double triazole biphenyl dicarboxylic acid copper complex monocrystalline of 1,4-dimethyl-2,5-two-1H-
Specificity generates 4 to fluorobenzoic boric acid, and the catalyst of 4'-DfBP is applied, and experimental result shows:
(1) catalyst that the complex monocrystal specificity in embodiment 2 generates 4,4'-DfBP to fluorobenzoic boric acid has relatively
Good catalytic effect, catalysis productivity reaches 96%；
(2) complex monocrystal is to 3-methoxyphenylboronic acid, 1-naphthalene phenylboric acid, 4-methylthio phenyl boric acid, 4-chlorophenylboronic acid, 4-pyrrole
Pyridine phenylboric acid catalytic effect does not the most even react.
The double triazole biphenyl dicarboxylic acid copper complex monocrystalline of a kind of 1,4-dimethyl-2,5-two-1H-disclosed by the invention is had
Some advantages and feature are:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) Isosorbide-5-Nitrae-dimethyl-2 prepared by the present invention, the double triazole biphenyl dicarboxylic acid copper complex monocrystalline of 5-bis--1H-,
Production cost is low, and method is easy, is suitable for large-scale production.Have in terms of catalysis generates 4,4'-DfBP to fluorobenzoic boric acid
Good catalytic effect.
Accompanying drawing explanation
The crystal structure figure of Fig. 1: complex monocrystal；
The tomograph of Fig. 2: complex monocrystal；
Fig. 3: 4,4'-DfBP1H NMR schemes.
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.Raw materials used it is commercially available.All raw materials are all public from chemical reagent both domestic and external
The raw materials such as department buys, such as Isosorbide-5-Nitrae-two bromo-2,5-dimethyl benzene, through continuation purification but directly do not use.
Embodiment 1
1,4-bis-bromo-2,5-dimethyl benzene: 1H-1,2,4-triazole: potassium carbonate: the mol ratio of copper oxide is 2:10:30:1
Be separately added in equipped with 50 mL three neck round bottom flasks of magneton, reflux condenser and thermometer CuO (0.0398 mg,
0.5 mmol), potassium carbonate (2.0731 g, 15 mmol), 1H-1,2,4-triazoles (0.345 mg, 5 mmol), Isosorbide-5-Nitrae-two
Bromo-2,5-dimethyl benzene (0.3360 g, 1 mmol), 20 mL DMF.Start stirring 100oC, reacts 24 hours.Reaction
After end, reactant liquor being down to room temperature, filter, filtrate adds 100 mL water, separates out a large amount of precipitation, sucking filtration, collects filter cake, yield
60%.Elementary analysis (C12N6H12) theoretical value (%): C, 59.99；H, 5.03；N, 34.98.Measured value: C, 60.02；H, 5.05；
N, 35.05；
1,4-bis-bromo-2,5-dimethyl benzene 1H-1,2,4-triazole.
The bromo-2,5-dimethyl benzene of the preferred 1,4-of the present invention bis-: 1H-1,2,4-triazole: potassium carbonate: the mol ratio of copper oxide is
2:10:30:1；Reaction temperature 80-200 DEG C, 12-120 hour response time.Use " one kettle way ", by bromo-for Isosorbide-5-Nitrae-two 2,5-bis-
Methylbenzene and 1H-1,2,4-triazoles prepare this organic compound in a heated condition, 1-(2,5-dimethyl-4-(1H-1,2,4-
Triazol-1-yl) phenyl)-1H-1,2,4-triazole (L).
Embodiment 2
1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole (L) (0.1 mmol), connection
Phthalic acid (bpdca) (0.1 mmol) and Cu (NO3)2·6H2O (0.1 mmol) is stirring half an hour in water (10 mL)
Rear filtration, filtrate room temperature obtains being suitable for the blue bulk crystals of X-ray single crystal diffraction after volatilizing two weeks.Productivity: 40%.Element divides
Analysis (C26H22CuN6O5) theoretical value (%): C, 55.56；H, 3.95；N, 14.95.Measured value: C, 55.49；H, 3.88；N,
14.87。
Embodiment 3
Crystal structure determination uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, and 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 crystal structure from difference Fourier electron density map, and through Lorentz lorentz and polarity effect correction.All of H is former
Son is synthesized by difference Fourier and determines through preferable position calculation.Detailed axonometry data:
Embodiment 4
Specificity is as the concrete instance of catalyst
Method: fluorobenzoic boric acid (0.82 mmol) and cesium carbonate (0.01 g) are dissolved in 3 mL DMF by replacement, add 5 mg
Catalyst, stirs 5 hours under room temperature, CH2Cl2Extraction, washing, it is dried, filters, precipitation, thick product is through petrol ether/ethyl acetate
Mixed liquor (v:v=1:1) by silica gel chromatography post affords product.
Result: obtaining 4,4'-DfBP 0.0756 g, calculated catalysis productivity is 97%.
Embodiment 5
Conclusion:
(1) the double triazole biphenyl dicarboxylic acid copper complex of 1,4-dimethyl-2,5-two-1H-is for catalytic substrate 4-methylthio phenyl boron
Acid does not play any catalytic action.
(2) the double triazole biphenyl dicarboxylic acid copper complex of 1,4-dimethyl-2,5-two-1H-for 3-methoxyphenylboronic acid,
1-naphthalene phenylboric acid, 4-chlorophenylboronic acid, 4-pyridine phenylboric acid catalytic effect general, catalysis productivity is between 2-11%.
(3) the double triazole biphenyl dicarboxylic acid copper complex of 1,4-dimethyl-2,5-two-1H-is for catalytic substrate 4-fluorobenzene boron
The catalytic effect of acid is best, and catalysis productivity is up to 97%.
After the preferred embodiment described in detail, it is familiar with this skilled worker and is clearly understood that, without departing from above-mentioned
Can carry out various change and amendment under claim and spirit, all technical spirit according to the present invention are to above example institute
Any simple modification, equivalent variations and the modification made, belongs to the scope of technical solution of the present invention.And the present invention is not illustrated
The restriction of example embodiment in book.
Claims (3)
1. Isosorbide-5-Nitrae-dimethyl-2, the monocrystalline of the double triazole biphenyl dicarboxylic acid copper complex of 5-bis--1H-, it is characterised in that this is single
Crystal structure uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, and λ=0.71073 is
Incident radiation, collects point diffraction with ω-2 θ scan mode, obtains cell parameter through least square refinement, from difference Fourier
Leaf electron density map utilizes software to solve single crystal data:
Its structure is as follows:
[Cu(L)(H2O) (bpdca)], wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Bpdca=biphenyl dicarboxylic acid.
2. the preparation side of the double triazole biphenyl dicarboxylic acid copper complex monocrystalline of 1,4-dimethyl-2,5-two-1H-described in claim 1
Method, it is characterised in that it is to use room temperature volatility process, i.e. L, bpdca and Cu (NO3)2·6H2O stirs mistake after half an hour in water
Filter, filtrate room temperature obtains being suitable for the blue bulk crystals of X-ray single crystal diffraction, wherein L:bpdca:Cu after volatilizing two weeks
(NO3)2·6H2The mol ratio of O is 1:1:1；
The structure of the double triazole biphenyl dicarboxylic acid copper complex monocrystalline of 1,4-dimethyl-2,5-two-1H-is [Cu (L) (H2O)
(bpdca)]；Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Bpdca=biphenyl dicarboxylic acid；
L bpdca。
3. the double triazole biphenyl dicarboxylic acid copper complex monocrystalline specificity pair of 1,4-dimethyl-2,5-two-1H-described in claim 1
Fluorobenzoic boric acid generates the application in terms of the catalyst of 4,4'-DfBP.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610255172.2A CN105837603A (en) | 2016-04-25 | 2016-04-25 | 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylbiphenyldicarboxylic acid copper complex monocrystal and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610255172.2A CN105837603A (en) | 2016-04-25 | 2016-04-25 | 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylbiphenyldicarboxylic acid copper complex monocrystal and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105837603A true CN105837603A (en) | 2016-08-10 |
Family
ID=56590194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610255172.2A Pending CN105837603A (en) | 2016-04-25 | 2016-04-25 | 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylbiphenyldicarboxylic acid copper complex monocrystal and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105837603A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004398A (en) * | 2019-12-23 | 2020-04-14 | 山西大学 | Microporous Cu-MOF material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497018A (en) * | 2014-12-15 | 2015-04-08 | 天津师范大学 | Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex |
| CN104513261A (en) * | 2014-12-15 | 2015-04-15 | 天津师范大学 | Oxylether bistriazole for catalysis of 4-tert-butylphenylboronic acid and preparation method thereof |
| CN104557980A (en) * | 2014-12-15 | 2015-04-29 | 天津师范大学 | Triazole-copper trifluoromethanesulfonate complex capable of catalyzing 4-tert-butylphenylboronic acid and preparation method of triazole-copper trifluoromethanesulfonate complex |
-
2016
- 2016-04-25 CN CN201610255172.2A patent/CN105837603A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497018A (en) * | 2014-12-15 | 2015-04-08 | 天津师范大学 | Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex |
| CN104513261A (en) * | 2014-12-15 | 2015-04-15 | 天津师范大学 | Oxylether bistriazole for catalysis of 4-tert-butylphenylboronic acid and preparation method thereof |
| CN104557980A (en) * | 2014-12-15 | 2015-04-29 | 天津师范大学 | Triazole-copper trifluoromethanesulfonate complex capable of catalyzing 4-tert-butylphenylboronic acid and preparation method of triazole-copper trifluoromethanesulfonate complex |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004398A (en) * | 2019-12-23 | 2020-04-14 | 山西大学 | Microporous Cu-MOF material and preparation method and application thereof |
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 | |
| CN105837603A (en) | 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylbiphenyldicarboxylic acid copper complex monocrystal and application thereof | |
| CN105713026A (en) | 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylterephthalic acid zinc complex monocrystal and application thereof | |
| CN105732719A (en) | 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole two-dimensional manganese complex single crystal and application | |
| CN105859755A (en) | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) isophthalic acid cadmium complex single crystal and application | |
| CN104513261A (en) | Oxylether bistriazole for catalysis of 4-tert-butylphenylboronic acid and preparation method thereof | |
| CN104402913B (en) | Double triazole-cupric perchlorate coordination compound of anthracene nucleus with catalysis phenylboric acid and preparation method thereof | |
| CN105859750A (en) | 1,4-dimethyl-2,5-bis-1H-double-triazole pyromellitic acid copper complex single crystal and application thereof | |
| CN105820181A (en) | 1,4-dimethyl-2,5-bis-1H-bis(triazole) three-dimensional copper complex single crystal and application | |
| CN105820193A (en) | 1,4-dimethyl-2,5-bis-1H-bis(triazole) cobalt pyromellitate complex single crystal and application | |
| CN105837605A (en) | 1, 4-dimethyl-2, 5-bi-1H-1, 2, 4-bis (triazol 1 yl) two-dimensional copper complex single crystal and application | |
| CN105859751A (en) | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) terephthalic acid copper complex single crystal and application | |
| CN105669711A (en) | 1, 4-dimethyl-2, 5-2-1H- bistriazole pyromellitic acid three-dimensional copper complex single-crystal and application | |
| CN105859756A (en) | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) cadmium mixed-ligand complex single crystal and application | |
| CN105859753A (en) | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) three-dimensional zinc complex single crystal and application | |
| CN105859786A (en) | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) 5-methylisophthalic acid manganese complex single crystal and application | |
| CN105859754A (en) | 1,4-dimethyl-2,5-bis-1H-1,2,4-double-triazole zinc mixed complex single crystal and application thereof | |
| CN105732668A (en) | 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole copper mixed complex single crystal and application | |
| CN104530097B (en) | Double triazole-tetrafluoro boric acid copper complex of anthracene nucleus with catalysis phenyl boric acid and preparation method thereof | |
| CN104557986B (en) | Have and be catalyzed triazole-copper triflate coordination compound to fluorobenzoic boric acid and preparation method thereof | |
| CN104497025B (en) | Have and be catalyzed double triazole-Tetrafluoroboric acid copper complex of the anthracene nucleus to methylphenylboronic 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 | |
| CN104557985B (en) | Oxygen ether dual-triazole copper complex capable of catalyzing p-fluorophenylboronic acid and preparation method of oxygen ether dual-triazole copper complex | |
| CN104478903B (en) | Anthracene-ring bitriazol-cupric tetrafluoroborate complex capable of catalyzing 3-methoxy phenylboronic acid and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160810 |