CN104557982A - Triazole-copper triflate complex with effect of catalyzing p-Tolylboronic acid and preparation method thereof - Google Patents
Triazole-copper triflate complex with effect of catalyzing p-Tolylboronic acid and preparation method thereof Download PDFInfo
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- CN104557982A CN104557982A CN201410767898.5A CN201410767898A CN104557982A CN 104557982 A CN104557982 A CN 104557982A CN 201410767898 A CN201410767898 A CN 201410767898A CN 104557982 A CN104557982 A CN 104557982A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ZIJDTDSIVOVKGW-UHFFFAOYSA-L copper 2H-triazole trifluoromethanesulfonate Chemical compound FC(S(=O)(=O)[O-])(F)F.[Cu+2].N1N=NC=C1.FC(S(=O)(=O)[O-])(F)F ZIJDTDSIVOVKGW-UHFFFAOYSA-L 0.000 title abstract description 3
- 230000000694 effects Effects 0.000 title abstract description 3
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 title abstract 3
- 239000010949 copper Substances 0.000 claims abstract description 31
- 150000004699 copper complex Chemical class 0.000 claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract 2
- 239000013078 crystal Substances 0.000 claims description 10
- -1 triazole copper complex Chemical class 0.000 claims description 7
- HVMMGTLUNJNHFE-UHFFFAOYSA-N 4-[3-(1,2,4-triazol-4-yl)phenyl]-1,2,4-triazole Chemical compound N=1N=CN(C1)C=1C=C(C=CC1)N1C=NN=C1 HVMMGTLUNJNHFE-UHFFFAOYSA-N 0.000 claims description 6
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000005260 alpha ray Effects 0.000 claims description 3
- 238000002447 crystallographic data Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229940018564 m-phenylenediamine Drugs 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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 Table
- 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
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a triazole-copper triflate complex with an effect of catalyzing p-Tolylboronic acid and a preparation method thereof. A hydrothermal method is adopted, and specifically the complex is prepared from Cu(CF3SO3)2 and L under the hydrothermal condition at the temperature of 100 DEG C. The invention further discloses an 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-triazole) serving as a coupled reaction catalyst of p-Tolylboronic 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)] (CF
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) and the application as the catalyst aspect to methylphenylboronic 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, this complex can be used as to be applied the catalyst of methylphenylboronic acid coupling reaction.
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:
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)] (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 monocrystalline, its feature in employing " hydro-thermal method ", at CH
3cN and H
2in O, by Cu (CF
3sO
3)
2with L ligand 1 60
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 60
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 application of the catalyst aspect of phenyl boric 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'-dimethyl diphenyl.
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, 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 160 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 160
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) 160
oc hydrothermal condition gets off to prepare copper complex { [Cu (L)] (CF
3sO
3) 0.33H
2o} (
1).Catalysis experiments proves, this complex can be used as to be applied the catalyst of methylphenylboronic acid coupling reaction.
1.1 g are taken to methylphenylboronic acid, 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'-dimethyl diphenyl.
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) as the application of the coupling reaction catalyst aspect to methylphenylboronic acid.
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