CN104447816B - There is catalysis triazole-Tetrafluoroboric acid copper complex to fluorobenzoic boric acid and preparation method thereof - Google Patents
There is catalysis triazole-Tetrafluoroboric acid copper complex to fluorobenzoic boric acid and preparation method thereof Download PDFInfo
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- CN104447816B CN104447816B CN201410769433.3A CN201410769433A CN104447816B CN 104447816 B CN104447816 B CN 104447816B CN 201410769433 A CN201410769433 A CN 201410769433A CN 104447816 B CN104447816 B CN 104447816B
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- triazole
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- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/08—Copper compounds
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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
- 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
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- 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
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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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
Abstract
The invention discloses one { [Cu (L)] (BF4)2·0.5H2O}? (<b>1</b>)? the preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) and fluorobenzoic boric acid coupling reaction is had potential using value as catalysis. It is to adopt " hydro-thermal method ", i.e. Cu (BF4)2With L 100?oC hydrothermal condition gets off to prepare this coordination compound. The present invention further discloses { [Cu (L)] (BF4)2·0.5H2O}? (<b>1</b>)? (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-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 (L)] (BF4)2·0.5H2The preparation method of O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) and the application as 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)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)] (BF4)2·0.5H2O} (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 copper complex { [Cu (L)] (BF of a kind of isophthalic is provided4)2·0.5H2O} (1) monocrystalline and preparation method thereof.
Following technical scheme is current inventor provides for this:
Double; two triazole copper complex { [Cu (L)] (BF of isophthalic4)2·0.5H2The 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.
The present invention further discloses double; two triazole copper complex { [Cu (L)] (BF of isophthalic4)2·0.5H2O} (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)] (BF of isophthalic of the present invention4)2·0.5H2The 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 (BF4)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 (BF4)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)] (BF of a kind of isophthalic4)2·0.5H2The 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 (BF4)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 (BF4)2It is 1:1 with the mol ratio of L;
Solvent of the present invention is mixed solvent, CH3CN and H2O。
Wherein Cu (BF4)2It is 1:1 with the mol ratio of L.
The present invention further discloses the double; two triazole copper complex of a kind of isophthalic and there is the catalysis effect to fluorobenzoic boric acid coupling reaction.
Double; two triazole copper complex { [Cu (L)] (BF of a kind of isophthalic disclosed by the invention4)2·0.5H2O} (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)] (BF prepared by the present invention4)2·0.5H2O} (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.
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 all buy from chemical reagents corporation both domestic and external, it does not have through continuation purify but directly use. Wherein Cu (BF4)2, CH3CN is 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(BF4)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 (BF4)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 (C10H9BCuF4N6O0.5) theoretical value (%): C, 32.32; H, 2.44; N, 22.62. Measured value: C, 32.35; H, 2.46; N, 22.69.
Embodiment 2
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 structure of coordination compound is shown in Fig. 2.
The crystallographic data of table 1 coordination compound 1
Embodiment 3
Cu(BF4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) mol ratio of (L) is 1:1;
We also attempted other ratios, such as Cu (BF4)2With-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazoles) mol ratio be 2:1, then the length of no matter hydro-thermal reaction time, all can not get crystalline compound. Therefore Cu (BF4)2With-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) mol ratio be 1:1 be 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)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)] (BF4)2·0.5H2O} (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 (2)
1. triazole-Tetrafluoroboric acid copper complex monocrystalline preparation as the application in the coupling reaction catalyst to fluorobenzoic boric acid, it is characterized in that this mono-crystalline structures adopts APEXIICCD single crystal diffractometer, using 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 wherein molecular formula of triazole-Tetrafluoroboric acid copper complex monocrystalline: [Cu (L)] (BF4)2·0.5H2O, L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazoles).
2. the application described in claim 1, it is characterised in that as the method for fluorobenzoic boric acid coupling reaction is as follows:
To fluorobenzoic boric acid 4,4'-DfBP
25mL beaker weighs 1g to fluorobenzoic boric acid, 0.2gCs2CO3, 3mLDMF and 0.1g catalyst complexes monocrystalline, to stir 1 hour under room temperature, TLC monitoring reacts completely, 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 4,4'-DfBPs.
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