CN104497018A - Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex - Google Patents
Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex Download PDFInfo
- Publication number
- CN104497018A CN104497018A CN201410767896.6A CN201410767896A CN104497018A CN 104497018 A CN104497018 A CN 104497018A CN 201410767896 A CN201410767896 A CN 201410767896A CN 104497018 A CN104497018 A CN 104497018A
- Authority
- CN
- China
- Prior art keywords
- triazole
- clo
- phenyl
- complex
- 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
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
- 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
-
- 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
-
- 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
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Abstract
The invention discloses a preparation method of {[Cu(L)] (ClO4).0.25H2O} (1) (L=4-(3-(4H-1, 2, 4-triazole-4-yl)phenyl)-4H-1, 2, 4-triazole). The complex is prepared by using a hydrothermal method comprising the step of reacting Cu(ClO4)2 and L under a 100-DEG C hydrothermal condition. The invention further discloses application of a copper complex, namely {[Cu(L)] (ClO4).0.25H2O} (1) (L=4-(3-(4H-1, 2, 4-triazole-4-yl)phenyl)-4H-1, 2, 4-triazole) as a catalyst for coupled reaction of p-fluorophenylboronic acid.
Description
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)] (ClO
4) 0.25H
2o} (
1) preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) and the application as the catalyzer aspect to fluorobenzoic boric acid linked 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 catalyzer to develop the organic synthesis of highly selective, 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, polymkeric substance, functional materials, liquid crystal, drug molecule and bioactive compounds.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 bridgingligands 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 mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
The present invention selects Cu (ClO
4)
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)] (ClO
4) 0.25H
2o} (
1).Catalysis experiments proves, this title complex can be used as to be applied the catalyzer of fluorobenzoic boric acid linked reaction.
Summary of the invention
Another object of the present invention is to provide a kind of isophthalic two triazole copper complex { [Cu (L)] (ClO
4) 0.25H
2o} (
1) monocrystalline and preparation method thereof.
Current inventor provides following technical scheme for this reason:
Two triazole copper complex { [Cu (L)] (ClO of isophthalic
4) 0.25H
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; L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole;
The present invention further discloses two triazole copper complex { [Cu (L)] (ClO of isophthalic
4) 0.25H
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 single crystal structure 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 unit cell parameters, utilize software to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex
1crystallographic data
Two triazole copper complex { [Cu (L)] (ClO of isophthalic of the present invention
4) 0.25H
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 " hydrothermal method ", at CH
3cN and H
2in O, by Cu (ClO
4)
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 (ClO
4)
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)] (ClO of a kind of isophthalic
4) 0.25H
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 " hydrothermal method ", at CH
3cN and H
2in O, by Cu (ClO
4)
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 (ClO
4)
2be 1:1 with the mol ratio of L;
Solvent of the present invention is mixed solvent, CH
3cN and H
2o.
Wherein Cu (ClO
4)
2be 1:1 with the mol ratio of L.
The present invention further discloses copper complex { [Cu (L)] (ClO
4) 0.25H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) as the application to fluorobenzoic boric acid coupling reaction catalyst aspect.
Two triazole copper complex { [Cu (L)] (ClO of a kind of isophthalic disclosed by the invention
4) 0.25H
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)] (ClO prepared by the present invention
4) 0.25H
2o}
n(
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 scale operation.
Accompanying drawing explanation
Fig. 1: title complex
1crystalline structure primitive figure;
Fig. 2: title complex
1tomograph;
The nuclear-magnetism figure of Fig. 3: 4,4'-DfBP.
Embodiment
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, through continuation purify but directly use.Raw materials used 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
In 50 mL, tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, add mphenylenediamine (1 mmol) respectively, two formyl hydrazine (2 mmol), starts and is stirred in 100 DEG C, reacts 12 hours.After reaction terminates, reaction solution is down to room temperature, separates out and precipitate in a large number, by precipitation water and ethyl alcohol recrystallization, yield 86%.Ultimate analysis C
10h
8n
6theoretical value: C, 56.60; H, 3.80; N, 39.60.Experimental value: C, 56.56; H, 3.75; N, 39.56.Mphenylenediamine, the mol ratio of two formyl hydrazine is 1:2.
Embodiment 2
Cu (ClO
4)
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 (ClO
4)
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).Ultimate analysis (C
10h
8.5clCuN
6o
4.25) theoretical value (%): C, 30.67; H, 2.03; N, 19.51.Measured value: C, 30.63; H, 2.06; N, 19.59.We also attempted other ratios, such as Cu (ClO
4)
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 (ClO
4)
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 unit cell parameters, utilize software to solve crystalline structure from difference Fourier electron density map through least-squares refinement, and through Lorentz lorentz and polarizing 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 title complex is shown in Fig. 2.
Table 1 title 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 catalyzer to develop the organic synthesis of highly selective, 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, polymkeric substance, functional materials, liquid crystal, drug molecule and bioactive compounds.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 bridgingligands 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 mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
The present invention selects Cu (ClO
4)
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)] (ClO
4) 0.25H
2o} (
1).Catalysis experiments proves, this title complex can be used as to be applied the catalyzer of fluorobenzoic boric acid linked reaction
1 g is taken to fluorobenzoic boric acid, 0.2 g Cs in 25 mL beakers
2cO
3, 3 mL DMF and 0.1 g catalyzer (title complex 1), stirred at ambient temperature 1 hour, TLC monitoring (PE:EA=1:1) reacts completely, 10 mLCH
2cl
220 mL distilled water washs are used again, organic phase sewage MgSO after extracted products
4drying, filter, precipitation, the thick product obtained strips post with sherwood oil, obtains 4,4'-DfBP.
Claims (4)
1. two triazole copper complex { [Cu (L)] (ClO of isophthalic
4) 0.25H
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.
2. the monocrystalline of copper complex described in claim 1, is characterized in that this single crystal structure 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 unit cell parameters, utilize software to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex
1crystallographic data
。
3. { [Cu (L)] (ClO of copper complex described in claim 1
4) 0.25H
2o}
n(
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 " hydrothermal method ", i.e. Cu (ClO
4)
2with L 100
oc hydrothermal condition gets off and prepares this title complex;
Described solvent is mixed solvent is CH
3cN and H
2o; Wherein Cu (ClO
4)
2be 1:1 with the mol ratio of L.
4. { [Cu (L)] (ClO of copper complex described in claim 1
4) 0.25H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) can be used as and applied the catalyzer of fluorobenzoic boric acid linked reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410767896.6A CN104497018B (en) | 2014-12-15 | 2014-12-15 | Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410767896.6A CN104497018B (en) | 2014-12-15 | 2014-12-15 | Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104497018A true CN104497018A (en) | 2015-04-08 |
| CN104497018B CN104497018B (en) | 2017-02-22 |
Family
ID=52938488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410767896.6A Expired - Fee Related CN104497018B (en) | 2014-12-15 | 2014-12-15 | Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104497018B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669711A (en) * | 2016-04-25 | 2016-06-15 | 天津师范大学 | 1, 4-dimethyl-2, 5-2-1H- bistriazole pyromellitic acid three-dimensional copper complex single-crystal and application |
| CN105669431A (en) * | 2016-04-25 | 2016-06-15 | 天津师范大学 | Three-dimensional manganese formate dehydrate complex single crystal and application |
| CN105713026A (en) * | 2016-04-25 | 2016-06-29 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylterephthalic acid zinc complex monocrystal and application thereof |
| CN105732719A (en) * | 2016-04-25 | 2016-07-06 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole two-dimensional manganese complex single crystal and application |
| CN105732668A (en) * | 2016-04-25 | 2016-07-06 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole copper mixed complex single crystal and application |
| CN105820193A (en) * | 2016-04-25 | 2016-08-03 | 天津师范大学 | 1,4-dimethyl-2,5-bis-1H-bis(triazole) cobalt pyromellitate complex single crystal and application |
| CN105820181A (en) * | 2016-04-25 | 2016-08-03 | 天津师范大学 | 1,4-dimethyl-2,5-bis-1H-bis(triazole) three-dimensional copper complex single crystal and application |
| 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 |
| CN105859756A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) cadmium mixed-ligand complex single crystal and application |
| CN105859754A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-bis-1H-1,2,4-double-triazole zinc mixed complex single crystal and application thereof |
| CN105859751A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) terephthalic acid copper complex single crystal and application |
| CN105859755A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) isophthalic acid cadmium complex single crystal and application |
| CN105859786A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) 5-methylisophthalic acid manganese complex single crystal and application |
| CN105859753A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) three-dimensional zinc complex single crystal and application |
| CN105859750A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-bis-1H-double-triazole pyromellitic acid copper complex single crystal and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356147A (en) * | 2014-11-10 | 2015-02-18 | 天津师范大学 | Triazole Cu-hypochlorite complex with potential ferroelectric functions and preparation method thereof |
-
2014
- 2014-12-15 CN CN201410767896.6A patent/CN104497018B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356147A (en) * | 2014-11-10 | 2015-02-18 | 天津师范大学 | Triazole Cu-hypochlorite complex with potential ferroelectric functions and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| N KIRAI ET AL: ""Homocoupling of Arylboronic Acids Catalyzed by 1,10-Phenanthroline-Ligated Copper Complexes in Air"", 《EUR. J. ORG. CHEM》 * |
| PILLAIYAR P. ET AL: ""Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal–organic frameworks"", 《GREEN 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 (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669711A (en) * | 2016-04-25 | 2016-06-15 | 天津师范大学 | 1, 4-dimethyl-2, 5-2-1H- bistriazole pyromellitic acid three-dimensional copper complex single-crystal and application |
| CN105669431A (en) * | 2016-04-25 | 2016-06-15 | 天津师范大学 | Three-dimensional manganese formate dehydrate complex single crystal and application |
| CN105713026A (en) * | 2016-04-25 | 2016-06-29 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bistriazolylterephthalic acid zinc complex monocrystal and application thereof |
| CN105732719A (en) * | 2016-04-25 | 2016-07-06 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole two-dimensional manganese complex single crystal and application |
| CN105732668A (en) * | 2016-04-25 | 2016-07-06 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole copper mixed complex single crystal and application |
| CN105820193A (en) * | 2016-04-25 | 2016-08-03 | 天津师范大学 | 1,4-dimethyl-2,5-bis-1H-bis(triazole) cobalt pyromellitate complex single crystal and application |
| CN105820181A (en) * | 2016-04-25 | 2016-08-03 | 天津师范大学 | 1,4-dimethyl-2,5-bis-1H-bis(triazole) three-dimensional copper complex single crystal and application |
| 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 |
| CN105859756A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) cadmium mixed-ligand complex single crystal and application |
| CN105859754A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-bis-1H-1,2,4-double-triazole zinc mixed complex single crystal and application thereof |
| CN105859751A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) terephthalic acid copper complex single crystal and application |
| CN105859755A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) isophthalic acid cadmium complex single crystal and application |
| CN105859786A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) 5-methylisophthalic acid manganese complex single crystal and application |
| CN105859753A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) three-dimensional zinc complex single crystal and application |
| CN105859750A (en) * | 2016-04-25 | 2016-08-17 | 天津师范大学 | 1,4-dimethyl-2,5-bis-1H-double-triazole pyromellitic acid copper complex single crystal and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104497018B (en) | 2017-02-22 |
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 | |
| CN104447816A (en) | Triazole and copper fluoroborate complex with p-fluorophenylboronic acid catalysis effect and preparation method of triazole and copper fluoroborate complex | |
| CN104497023B (en) | There is the two triazole-Tetrafluoroboric acid copper complex of anthracene nucleus and its preparation method of catalysis 4-pyridine phenylo boric acid | |
| CN104447810B (en) | Triazole-copper triflate title complex with catalysis 3-methoxyphenylboronic acid and preparation method thereof | |
| CN104497022B (en) | Triazole-cupric perchlorate title complex with catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof | |
| CN104478902B (en) | Triazole-Tetrafluoroboric acid copper complex with catalysis 3-methoxyphenylboronic acid and preparation method thereof | |
| CN104530096B (en) | Triazole-Tetrafluoroboric acid copper complex with catalysis 4-pyridine phenylo boric acid and preparation method thereof | |
| CN104447807B (en) | Triazole-Tetrafluoroboric acid copper complex with catalysis phenylo boric 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 | |
| CN104530097A (en) | Anthracycline bis-triazole-copper tetrafluoroborate complex for catalyzing phenylboronic acid and preparation method thereof | |
| CN104497024A (en) | Triazole-copper perchlorate complex with 3-methoxyphenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex | |
| CN104447808A (en) | Triazole-copper perchlorate complex capable of catalyzing phenylboronic acid and preparation method of complex | |
| CN104497020A (en) | Triazole and copper perchlorate complex with 4-pyridinylphenylboronic acid catalyzing effect and preparation method of triazole and copper perchlorate complex | |
| CN104530094A (en) | Triazole-copperperchlorate hydrate complex for catalyzing 4-methoxyphenylboronic acid and preparation method thereof | |
| CN104478903A (en) | Anthracene-ring bitriazol-cupric tetrafluoroborate complex capable of catalyzing 3-methoxy phenylboronic acid and preparation method thereof | |
| CN104447812A (en) | Triazole and copper perchlorate complex with p-tolylboronic acid catalysis effect and preparation method of triazole and copper perchlorate complex | |
| CN104447814A (en) | Anthracycline bitriazole and copper fluoroborate complex with 4-methoxyphenylboronic acid catalysis effect and preparation method of anthracycline bitriazole and copper fluoroborate complex | |
| CN104478904A (en) | Anthracene-ring bitriazol-cupric tetrafluoroborate complex capable of catalyzing 4-tert-butyl phenylboronic 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 | |
| CN104497021A (en) | Triazole and copper fluoroborate complex with 4-methoxyphenylboronic acid catalyzing effect and preparation method of triazole and copper fluoroborate complex | |
| CN104447815A (en) | Triazole and copper fluoroborate complex with 4-tert-butylphenylboronic acid catalysis effect and preparation method of triazole and copper fluoroborate complex |
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 |
Granted publication date: 20170222 Termination date: 20171215 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |