CN104447809B - There is catalysis double; two triazole-Tetrafluoroboric acid copper complex of anthracene nucleus to fluorobenzoic boric acid and preparation method thereof - Google Patents
There is catalysis double; two triazole-Tetrafluoroboric acid copper complex of anthracene nucleus to fluorobenzoic boric acid and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000004327 boric acid Substances 0.000 title claims abstract description 11
- 150000001454 anthracenes Chemical class 0.000 title claims abstract description 10
- -1 triazole-Tetrafluoroboric acid copper Chemical compound 0.000 title claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 title abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract 2
- 238000002447 crystallographic data Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 150000003852 triazoles Chemical class 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 150000004699 copper complex Chemical class 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical class C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical class C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910017981 Cu(BF4)2 Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 230000005260 alpha ray Effects 0.000 description 2
- 230000000975 bioactive effect Effects 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
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000003446 ligand Substances 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
- 239000012046 mixed solvent Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 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
- 208000035126 Facies Diseases 0.000 description 1
- 238000004458 analytical method Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 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
- 239000003208 petroleum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time 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
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- 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
- B01J31/18—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
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- 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
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- 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
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- 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 Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to and there is catalysis to double; two triazole-Tetrafluoroboric acid copper complex of the anthracene nucleus of fluorobenzoic boric acid and preparation method thereof, disclose one { [Cu (tatrz)2(H2O)2](BF4)2(<b>1</b>) preparation method of (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) and fluorobenzoic boric acid coupling reaction is had potential using value as catalysis. It is to adopt " room temperature volatility process ", i.e. Cu (BF4)2Get off to prepare this coordination compound with tatrz stirring at normal temperature volatilization condition. The present invention further discloses { [Cu (tatrz)2(H2O)2](BF4)2(<b>1</b>) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) can as the application of the coupling reaction catalyst aspect to fluorobenzoic boric 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 (tatrz)2(H2O)2](BF4)2(1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) preparation method and as the application of the catalyst aspect to fluorobenzoic boric 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 (BF4)2Under normal temperature condition, copper complex { [Cu (tatrz) is prepared with 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz)2(H2O)2](BF4)2(1). Catalysis experiments proves, this coordination compound can be applied as to the catalyst of fluorobenzoic boric acid coupling reaction.
Summary of the invention
Offer double; two triazole the copper complex { [Cu (tatrz) of a kind of anthracene nucleus is provided2(H2O)2](BF4)2(1) monocrystalline and preparation method thereof.
Following technical scheme is current inventor provides for this:
Double; two triazole the copper complex { [Cu (tatrz) of anthracene nucleus2(H2O)2](BF4)2(1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) structural motif as shown in Figure 1.
The present invention further discloses double; two triazole the copper complex { [Cu (tatrz) of anthracene nucleus2(H2O)2](BF4)2(1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-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 (��=0.71073), point diffraction is collected with ��-2 �� 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 the copper complex { [Cu (tatrz) of anthracene nucleus of the present invention2(H2O)2](BF4)2The preparation method of (1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazoles) monocrystalline, its feature is adopt " room temperature volatility process " at it, i.e. Cu (BF4)2Get off to obtain being suitable for the yellow rhabdolith of X-ray single crystal diffraction with tatrz stirring at normal temperature volatilization condition. Wherein CH3CN and H2The volume ratio of O is 4:6, Cu (BF4)2It is 1:1 with the mol ratio of tatrz;
The more detailed preparation method of the present invention is as follows:
Double; two triazole the copper complex { [Cu (tatrz) of a kind of anthracene nucleus2(H2O)2](BF4)2The preparation method of (1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazoles) monocrystalline, its feature adopts " room temperature volatility process " at it, i.e. Cu (BF4)2Get off to obtain being suitable for the yellow rhabdolith of X-ray single crystal diffraction with tatrz stirring at normal temperature volatilization condition. Wherein CH3CN and H2The volume ratio of O is 4:6, Cu (BF4)2It is 1:1 with the mol ratio of tatrz;
Solvent of the present invention is mixed solvent, CH3CN and H2O��
Wherein Cu (BF4)2It is 1:1 with the mol ratio of tatrz.
The present invention further discloses the double; two triazole copper complex of a kind of anthracene nucleus and there is the catalysis effect to fluorobenzoic boric acid coupling reaction.
Double; two triazole the copper complex { [Cu (tatrz) of a kind of anthracene nucleus disclosed by the invention2(H2O)2](BF4)2(1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-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 (tatrz) prepared by the present invention2(H2O)2](BF4)2(1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazoles) production cost is low, 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;
The nuclear-magnetism figure of Fig. 3: 4,4'-DfBP.
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 such as: anthracene nucleus etc. are all buy from chemical reagents corporation both domestic and external, it does not have through continuing to purify but directly use. Wherein Cu (BF4)2, CH3CN is by commercially available.
Embodiment 1
The preparation of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz) part
1-of the present invention [9-(1H-1,2,4-triazole-1-base) anthracene-10-base] preparation method of-1H-1,2,4-triazoles, its feature is adopting " one kettle way ", in polar solvent, by 9,10-dibromoanthracenes, triazole, potassium carbonate and copper oxide prepare this organic compound in a heated condition; Wherein 9,10-dibromoanthracene: triazole: potassium carbonate: the mol ratio of copper oxide is 2:10:30:1;
The preferred 9,10-dibromoanthracene (I) of the present invention: triazole (II): potassium carbonate: the mol ratio of copper oxide is 2:10:30:1; Reaction temperature 80-200 DEG C, 12-120 hour response time.
The more detailed preparation method of the present invention is as follows:
A kind of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base] preparation method of-1H-1,2,4-triazoles is characterized in that, in polar solvent, adopt " one kettle way ", by 9,10-dibromoanthracenes, triazole, potassium carbonate and copper oxide prepare this organic compound in a heated condition;
Polar solvent of the present invention is DMF.
Wherein 9,10-dibromoanthracene: triazole: potassium carbonate: the mol ratio of copper oxide is 2:10-15:30:1;
Embodiment 2
Cu(BF4)2It is 1:1 with the mol ratio of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz);
Tatrz (0.0624g, 0.2mmol) and Cu (BF4)2(0.0691g, 0.2mmol) is at H2O (6mL) and CH3In the mixed solvent of CN (4mL), stirring at normal temperature filtered after half an hour, the yellow rhabdolith that filtrate room temperature volatilization X-ray single crystal diffraction is analyzed. Productivity: 35% (calculating based on tatrz). Elementary analysis (C36H28B2CuF8N12O2) theoretical value (%): C, 48.16; H, 3.14; N, 18.72. Measured value: C, 48.15; H, 3.16; N, 18.69.
Embodiment 2
Crystal structure determination adopts APEXIICCD single crystal diffractometer, use is incident radiation through graphite monochromatised Mok alpha ray (��=0.71073), point diffraction is collected with ��-2 �� 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 3
Cu(BF4)2It is 1:1 with the mol ratio of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz);
We also attempted other ratios, such as Cu (BF4)2Be 2:1 with the mol ratio of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazoles (tatrz), then the length of no matter hydro-thermal reaction time, all can not get crystalline compound. Therefore Cu (BF4)2Be 1:1 with the mol ratio of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz) it is optimum response proportioning.
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 (BF4)2Copper complex { [Cu (tatrz) is prepared when room temperature volatilization with 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz)2(H2O)2](BF4)2(1). Catalysis experiments proves, this coordination compound can be applied as to the catalyst of fluorobenzoic boric acid coupling reaction.
25mL beaker weighs 1g to fluorobenzoic boric 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 4,4'-DfBPs.
Claims (1)
1. the double; two triazole copper complex monocrystalline of anthracene nucleus in preparation as the application in the coupling reaction catalyst to fluorobenzoic boric acid, the molecular formula of its anthracene nucleus pair triazole copper complex monocrystalline: [Cu (tatrz)2(H2O)2](BF4)2, tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazoles; The crystallographic data of its coordination compound is as follows:
��
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