CN104447808B - Triazole-cupric perchlorate coordination compound with catalysis phenylboric acid and preparation method thereof - Google Patents
Triazole-cupric perchlorate coordination compound with catalysis phenylboric acid and preparation method thereof Download PDFInfo
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- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 title abstract description 13
- 238000006555 catalytic reaction Methods 0.000 title description 8
- 239000010949 copper Substances 0.000 claims abstract description 28
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- -1 triazole copper complex Chemical class 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000005260 alpha ray Effects 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 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
- 238000003756 stirring Methods 0.000 claims description 3
- 208000035126 Facies Diseases 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 abstract description 18
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 abstract description 18
- 150000004699 copper complex Chemical class 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 5
- 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 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
- 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
- 239000000047 product Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-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
- 241001597008 Nomeidae Species 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
- 238000002447 crystallographic data 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
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 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
- 230000008569 process Effects 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 239000002994 raw material Substances 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
- 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
- 230000000694 effects Effects 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
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000002244 precipitate 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
- 230000004044 response Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012549 training 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
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—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
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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 one { [Cu (L)] (ClO4)·0.25H2O} (<b>1</b>) preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole). It is to adopt " hydro-thermal method ", i.e. Cu (ClO4)2With L 100oC hydrothermal condition gets off to prepare this coordination compound. The present invention further discloses copper complex { [Cu (L)] (ClO4)·0.25H2O} (<b>1</b>) (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 of phenylboric 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)] (ClO4)·0.25H2The application of the preparation method of O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) and the catalyst aspect as phenylboric acid coupling reaction.
Background technology
The research carrying out high selectivity with transition metal complex catalysis is always up an active field. Be difficult to the reaction realized with common synthesizing mean, busy use transition metal complex can a step complete in a mild condition.Therefore, adopt metal complex to make catalyst to develop the organic synthesis of high selectivity, high conversion, be very interesting problem. In organic synthesis, general conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex demonstrates multiformity 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 expensive palladium catalyst can be replaced with cheap copper complex, it is achieved the process of reaction, it is possible not only to save cost, and is expected to industrialized production.
1,2,4-triazole and derivant thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridging ligands that coordination ability is stronger, have synthesized and characterized substantial amounts of monokaryon, multinuclear and multidimensional compound at present. These parts can with 1, nitrogen-atoms on 2 forms N1 with metallic ion coordination, N2-bridge gang mould formula, for 4 unsubstituted 1,2,4-triazole derivative can pass through 2, nitrogen-atoms on 4 forms N2, N4-bridge gang mould formula, this N2, N4-bridge gang mould formula is similar with N1, the N3-bridge gang mould formula of imidazoles in metalloenzyme. Specific use for triazole class compounds is also manifested by the design of molecular device, and it has been the vital step of device that synthesis has the metal complex of different dimension.
The present invention selects Cu (ClO4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100oC hydrothermal condition gets off to prepare copper complex { [Cu (L)] (ClO4)·0.25H2O} (1). Catalysis experiments proves, this coordination compound can be applied as the catalyst of phenylboric acid coupling reaction.
Summary of the invention
Offer double; two triazole copper complex { [Cu (L)] (ClO of a kind of isophthalic is provided4)·0.25H2O} (1) monocrystalline and preparation method thereof.
Following technical scheme is current inventor provides for this:
Double; two triazole copper complex { [Cu (L)] (ClO of isophthalic4)·0.25H2The structural motif of O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) is 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 double; two triazole copper complex { [Cu (L)] (ClO of isophthalic4)·0.25H2O} (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 APEXIICCD single crystal diffractometer, use is incident radiation through graphite monochromatised Mok alpha ray (λ=0.71073), point diffraction is collected with ω-2 θ scan mode, obtain cell parameter through least square refinement, utilize software to solve single crystal data from difference Fourier electron density map:
The crystallographic data of table 1. coordination compound 1
Double; two triazole copper complex { [Cu (L)] (ClO of isophthalic of the present invention4)·0.25H2The preparation method of O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazoles) monocrystalline, its feature is adopting " hydro-thermal method ", at CH3CN and H2In O, by Cu (ClO4)2With L ligand 1 00oReact under C hydrothermal condition, obtain being suitable for the yellow rhabdolith of X-ray single crystal diffraction. Wherein CH3CN and H2The volume ratio of O is 4:6, Cu (ClO4)2It is 1:1 with the mol ratio of L;
The more detailed preparation method of the present invention is as follows:
Double; two triazole copper complex { [Cu (L)] (ClO of a kind of isophthalic4)·0.25H2The preparation method of O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazoles) monocrystalline, its feature is adopting " hydro-thermal method ", at CH3CN and H2In O, by Cu (ClO4)2With L ligand 1 00oReact under C hydrothermal condition, obtain being suitable for the yellow rhabdolith of X-ray single crystal diffraction.Wherein CH3CN and H2The volume ratio of O is 4:6, Cu (ClO4)2It is 1:1 with the mol ratio of L;
Solvent of the present invention is mixed solvent, CH3CN and H2O。
Wherein Cu (ClO4)2It is 1:1 with the mol ratio of L.
The present invention further discloses copper complex { [Cu (L)] (ClO4)·0.25H2O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) is as the application of phenylboric acid coupling reaction catalyst aspect.
Double; two triazole copper complex { [Cu (L)] (ClO of a kind of isophthalic disclosed by the invention4)·0.25H2O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline have the advantage that and being characterized in that:
(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 invention4)·0.25H2O}n(1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazoles) production cost is low, and method is easy, is suitable for large-scale production.
Accompanying drawing explanation
Fig. 1: the crystal structure primitive figure of coordination compound 1;
Fig. 2: the tomograph of coordination compound 1;
Fig. 3: the nuclear-magnetism figure of biphenyl.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, and embodiment is only indicative, is in no way to be construed as the scope that it is intended to limit the present invention in any manner. All of raw material is all buy from chemical reagents corporation both domestic and external, it does not have 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 equipped with tri-mouthfuls of round-bottomed flasks of 50mL of magneton, reflux condenser and thermometer, it is separately added into m-diaminobenzene. (1mmol), double; two formylhydrazines (2mmol), starts stirring at 100 DEG C, react 12 hours. After reaction terminates, reactant liquor is down to room temperature, precipitates out a large amount of precipitation, by precipitation water and ethyl alcohol recrystallization, yield 86%. Elementary analysis C10H8N6Theoretical value: C, 56.60; H, 3.80; N, 39.60. Experiment value: C, 56.56; H, 3.75; N, 39.56. M-diaminobenzene., the mol ratio of double; two formylhydrazines is 1:2.
Embodiment 2
Cu(ClO4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) mol ratio of (L) is 1:1;
L (0.0424g, 0.2mmol), Cu (ClO4)2(0.0691g, 0.2mmol), H2O (6mL), CH3CN (4mL), hydro-thermal 100oC was slowly dropped to room temperature after tri-days. The yellow rhabdolith that applicable X-ray single crystal diffraction is analyzed is had after driving still. Productivity: 35% (calculating based on L). Elementary analysis (C10H8.5ClCuN6O4.25) 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 (ClO4)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 (ClO4)2Be 1:1 with the mol ratio of L it is optimum response proportioning.
Embodiment 3
Crystal structure determination adopts APEXIICCD single crystal diffractometer, use is incident radiation through graphite monochromatised Mok alpha ray (λ=0.71073), point diffraction is collected with ω-2 θ scan mode, cell parameter is obtained 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 atom is synthesized by difference Fourier and determines through desirable position calculation. Detailed axonometry data are in Table 1.Structural motif is shown in Fig. 1, and the three dimensional structure of coordination compound is shown in Fig. 2.
The crystallographic data of table 1 coordination compound 1
Embodiment 4
The research carrying out high selectivity with transition metal complex catalysis is always up an active field. Be difficult to the reaction realized with common synthesizing mean, busy use transition metal complex can a step complete in a mild condition. Therefore, adopt metal complex to make catalyst to develop the organic synthesis of high selectivity, high conversion, be very interesting problem. In organic synthesis, general conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex demonstrates multiformity 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 expensive palladium catalyst can be replaced with cheap copper complex, it is achieved the process of reaction, it is possible not only to save cost, and is expected to industrialized production.
1,2,4-triazole and derivant thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridging ligands that coordination ability is stronger, have synthesized and characterized substantial amounts of monokaryon, multinuclear and multidimensional compound at present. These parts can with 1, nitrogen-atoms on 2 forms N1 with metallic ion coordination, N2-bridge gang mould formula, for 4 unsubstituted 1,2,4-triazole derivative can pass through 2, nitrogen-atoms on 4 forms N2, N4-bridge gang mould formula, this N2, N4-bridge gang mould formula is similar with N1, the N3-bridge gang mould formula of imidazoles in metalloenzyme. Specific use for triazole class compounds is also manifested by the design of molecular device, and it has been the vital step of device that synthesis has the metal complex of different dimension.
The present invention selects Cu (ClO4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100oC hydrothermal condition gets off to prepare copper complex { [Cu (L)] (ClO4)·0.25H2O} (1). Catalysis experiments proves, this coordination compound can be applied as the catalyst of phenylboric acid coupling reaction.
25mL beaker weighs 1g phenylboric acid, 0.2gCs2CO3, 3mLDMF and 0.1g catalyst (coordination compound 1), stir 1 hour under room temperature, TLC monitoring (PE:EA=1:1) reacts completely, 10mLCH2Cl220mL distilled water wash, organic facies sewage MgSO is used again after extracted products4Dry, filter, precipitation, the thick product obtained strips post with petroleum ether, obtains biphenyl.
Claims (2)
1. the double; two triazole copper complex monocrystalline of isophthalic in preparation as the application in phenylboric acid coupling reaction catalyst, it is characterized in that this mono-crystalline structures adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha ray, λ=0.71073 is incident radiation, point diffraction is collected with ω-2 θ scan mode, obtain cell parameter through least square refinement, utilize software to solve single crystal data from difference Fourier electron density map:
The molecular formula of the double; two triazole copper complex monocrystalline of described isophthalic: [Cu (L)] (ClO4)·0.25H2O, wherein L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazoles.
2. application according to claim 1, wherein the method for phenylboric acid coupling reaction is as follows:
25mL beaker weighs 1g phenylboric acid, 0.2gCs2CO3, 3mLDMF and 0.1g catalyst complexes monocrystalline, stir 1 hour under room temperature, TLC monitors, 10mLCH2Cl220mL distilled water wash, the anhydrous MgSO of organic facies is used again after extracted products4Dry, filter, precipitation, the thick product obtained strips post with petroleum ether, obtains biphenyl.
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Non-Patent Citations (5)
| Title |
|---|
| Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal–organic frameworks;Kasi Pitchumani et al.;《Green Chemistry》;20140224;第16卷;第2865-2875页 * |
| Clay encapsulated Cu(OH)xpromoted homocoupling of arylboronic acids: An efficient and eco-friendly protocol;Baldev Singh et al.;《Applied Catalysis A:General》;20131108;第470卷;第232-238页 * |
| Homocoupling of Arylboronic Acids Catalyzed by 1,10-Phenanthroline-Ligated Copper Complexes in Air;N Kirai et al.;《Eur. J. Org. Chem.》;20091231;第12卷;第1864-1867页 * |
| Synthesis，Crystal Structure，and Properties of a 3D Cu(I) Coordination Polymer Based on Cu3(CN)2 Clusters and 1,3-Di-(1,2,4-Triazole-4-yl)Benzene;Shao-Bin Miao et al.;《J Clust Sci.》;20140202;第25卷;第1137-1145页 * |
| Two novel 3D porous Copper(II) and Zinc(II) frameworks with 1,3-di-(1,2,4- triazole-4-yl)benzene: 4-connected dmp network versus 6-connnectedα-Po network based on trinuclear Zinc(II) clusters;Xia Qin et al.;《Inorganic Chemistry Communications》;20131003;第37卷;第166-169页 * |
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