CN104557987B - Double triazole copper complex of oxygen ether with catalysis phenyl boric acid and preparation method thereof - Google Patents
Double triazole copper complex of oxygen ether with catalysis phenyl boric acid and preparation method thereof Download PDFInfo
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- CN104557987B CN104557987B CN201410769312.9A CN201410769312A CN104557987B CN 104557987 B CN104557987 B CN 104557987B CN 201410769312 A CN201410769312 A CN 201410769312A CN 104557987 B CN104557987 B CN 104557987B
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- triazole
- boric acid
- phenyl
- phenyl boric
- copper complex
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Abstract
The invention discloses a kind of double triazole copper complex of oxygen ether with catalysis phenyl boric acid and preparation method thereof.It is to use " normal temperature volatility process ", i.e. Cu (NO3)2Get off to prepare this complex with L stirring at normal temperature volatilization condition.The present invention further discloses [Cu (L)2(NO3)2] (1) (L=1 (4 (4 (1H 1,2,4 triazole 1 base) phenoxy group) phenyl) 1H 1,2,4 triazole) can be as the application in terms of the coupling reaction catalyst of phenyl 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 subsidizes (TD12-5038).
Technical field
The invention belongs to Inorganic synthese technical field, relate to copper complex [Cu (L)2(NO3)2] (1) (L = 1-(4-
(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) preparation method and as phenyl boric acid
Application in terms of the catalyst of coupling reaction.
Background technology
The research carrying out high selectivity with transition metal complex catalysis is always an active field.With commonly
Synthesizing mean is difficult to the reaction realizing, busy use transition metal complex can a step complete in a mild condition.Therefore, adopt
Do, with metal complex, the organic synthesis that catalyst develops 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 many
Sample catalysis.Palladium catalysed cross coupling reaction species is a lot, and these reactions are at synthesis of natural product, polymer, functional material, liquid
Crystalline substance, drug molecule and bioactive compound all have been widely used.But palladium catalyst is relatively costly, if can be with cheap
Copper complex replaces expensive palladium catalyst, it is achieved the process of reaction, is possible not only to cost-effective, and is expected to industry metaplasia
Produce.
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are that the bridging that coordination ability is stronger is joined
Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound at present.These parts can be former with the nitrogen on 1,2
Son and metallic ion coordination form N1, N2-bridging pattern, can pass through 2,4 for 4 unsubstituted 1,2,4-triazole derivatives
On nitrogen-atoms formed N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, N3-bridging pattern
Similar.Specific use for triazole class compounds is also manifested by the design of molecular device, and synthesis has different dimension
Metal complex is to complete the vital step of device.
The present invention is i.e. to select Cu (NO3)2With 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-
1,2,4-triazole (L) prepares copper complex [Cu (L) under normal temperature condition2(NO3)2] (1).Catalysis experiments proves, this is joined
Compound can be applied as the catalyst of phenyl boric acid coupling reaction.
Content of the invention
The double triazole copper complex [Cu (L) of a kind of isophthalic of offer is provided2(NO3)2] (1) monocrystalline
And preparation method thereof.
Current inventor provides following technical scheme for this:
The double triazole copper complex [Cu (L) of oxygen ether2(NO3)2] (1) (L=1-(4-(4-(1H-1,2,4-triazole-1-
Base) phenoxy group) phenyl)-1H-1,2,4-triazole) structural motif as shown in Figure 1.
The present invention further discloses the double triazole copper complex [Cu (L) of oxygen ether2(NO3)2] (1) (L = 1-(4-(4-
(1H-1,2,4-triazole-1-bases) phenoxy group) phenyl)-1H-1,2,4-triazoles) monocrystalline, it is characterised in that this monocrystalline tie
Structure uses APEX II CCD single crystal diffractometer, and it is incident for using through graphite monochromatised Mok alpha ray (λ=0.71073)
Radiation, withω-2θScan mode collects point diffraction, obtains cell parameter through least square refinement, from difference Fourier electricity
Sub-density map utilizes software to solve single crystal data:
The crystallographic data of table 1. complex 1
The double triazole copper complex [Cu (L) of oxygen ether of the present invention2(NO3)2] (1) (L = 1-(4-(4-(1H-1,2,4-
Triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazoles) preparation method of monocrystalline, its feature is to use " normal temperature at it
Volatility process ", i.e. Cu (NO3)2Get off to obtain being suitable for the yellow rhabdolith of X-ray single crystal diffraction with L stirring at normal temperature volatilization condition.
Wherein CH3OH and H2The volume ratio of O is 4:6, Cu (NO3)2Mol ratio with L is 1:1；
The more detailed preparation method of the present invention is as follows:
The double triazole copper complex [Cu (L) of a kind of oxygen ether2(NO3)2] (1) (L=1-(4-(4-(1H-1,2,4-tri-nitrogen
Azoles-1-base) phenoxy group) phenyl)-1H-1,2,4-triazoles) preparation method of monocrystalline, its feature uses at it that " normal temperature volatilizees
Method ", i.e. Cu (NO3)2Get off to obtain being suitable for the yellow rhabdolith of X-ray single crystal diffraction with L stirring at normal temperature volatilization condition.Wherein
CH3OH and H2The volume ratio of O is 4:6, Cu (NO3)2Mol ratio with L is 1:1；
Solvent of the present invention is mixed solvent, CH3OH and H2O。
Wherein Cu (NO3)2Mol ratio with L is 1:1.
The present invention further discloses the double triazole copper complex of a kind of oxygen ether and there is the effect of catalysis phenyl boric acid coupling reaction.
The double triazole copper complex [Cu (L) of a kind of oxygen ether disclosed by the invention2(NO3)2] (1) (L = 1-(4-(4-(1H-
1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) monocrystalline had the advantage that to be with feature:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) [the Cu (L) prepared by the present invention2(NO3)2] (1) (L=1-(4-(4-(1H-1,2,4-triazole-1-
Base) phenoxy group) phenyl)-1H-1,2,4-triazoles) production cost is low, and method is easy, is suitable for large-scale production.
Brief description
The crystal structure primitive figure of Fig. 1: complex 1；
The one-dimensional catenary structure figure of Fig. 2: complex 1.
The nuclear-magnetism figure of Fig. 3: biphenyl.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, and embodiment is only explanatory, is in no way intended to it
Limit the scope of the present invention by any way.All of raw material is all to buy from chemical reagents corporation both domestic and external, does not has
Through continuation purification but directly use.Wherein Cu (NO3)2, CH3OH is by commercially available.
Embodiment 1
The preparation of 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L)
1-of the present invention (4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole
Preparation method, its feature use " one kettle way ", in polar solvent, by 1,1,2,2-tetra-(4-bromophenyl) ethene, triazole,
This organic compound prepared in a heated condition by potassium carbonate and cupric oxide；Wherein 4,4 '-dibromodiphenyl ether: triazole: potassium carbonate: oxygen
The mol ratio changing copper is 2:10:30:1；
The present invention preferably 4,4 '-dibromodiphenyl ether: triazole: potassium carbonate: the mol ratio of cupric oxide is 2:10:30:1；Reaction
Temperature 80-200 DEG C, reaction time 12-120 hour.
The more detailed preparation method of the present invention is as follows:
A kind of preparation of 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole
Method is characterized in that, in polar solvent, uses " one kettle way ", by 4,4 '-dibromodiphenyl ether, triazole, potassium carbonate and oxidation
Copper prepares this organic compound in a heated condition；
Embodiment 2
Cu(NO3)2With 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole
(L) mol ratio is 1:1；
L (0.0304 g, 0.1 mmol) and Cu (NO3)2(0.0242 g, 0.1 mmol) is at H2O (6 mL) and
CH3In the mixed solvent of OH (4 mL), stirring at normal temperature filtered after half an hour, and filtrate normal temperature volatilization X-ray single crystal diffraction is analyzed
Yellow rhabdolith.Productivity: 45% (calculating based on L).Elementary analysis (C32H24CuN14O8) theoretical value (%): C, 48.27；H,
3.04；N, 24.63.Measured value: C, 48.25；H, 3.16；N, 24.66.
Embodiment 2
Crystal structure determination uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray (λ
=0.71073) it is incident radiation, withω-2θScan mode collects point diffraction, obtains structure cell through least square refinement
Parameter, utilizes software to solve crystal structure from difference Fourier electron-density map, and through Lorentz lorentz and polarity effect correction.All
H atom synthesized and determined through preferable position calculation by difference Fourier.Detailed axonometry data are shown in Table 1.Structural motif
Seeing Fig. 1, one-dimensional catenary structure is shown in Fig. 2.
The crystallographic data of table 1. complex 1
Embodiment 3
Cu(NO3)2With 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole
(L) mol ratio is 1:1；
We also attempted other ratios, such as Cu (NO3)2With 1-(4-(4-(1H-1,2,4-triazole-1-base) benzene oxygen
Base) phenyl)-1H-1, the mol ratio of 2,4-triazoles (L) is 2:1, then the length of no matter hydro-thermal reaction time, all cannot get crystalline substance
State compound.Therefore Cu (NO3)2With 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-three
The mol ratio of nitrogen azoles (L) be 1:1 be optimum response proportioning.
Embodiment 4
The research carrying out high selectivity with transition metal complex catalysis is always an active field.With commonly
Synthesizing mean is difficult to the reaction realizing, busy use transition metal complex can a step complete in a mild condition.Therefore, adopt
Do, with metal complex, the organic synthesis that catalyst develops 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 many
Sample catalysis.Palladium catalysed cross coupling reaction species is a lot, and these reactions are at synthesis of natural product, polymer, functional material, liquid
Crystalline substance, drug molecule and bioactive compound all have been widely used.But palladium catalyst is relatively costly, if can be with cheap
Copper complex replaces expensive palladium catalyst, it is achieved the process of reaction, is possible not only to cost-effective, and is expected to industry metaplasia
Produce.
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are that the bridging that coordination ability is stronger is joined
Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound at present.These parts can be former with the nitrogen on 1,2
Son and metallic ion coordination form N1, N2-bridging pattern, can pass through 2,4 for 4 unsubstituted 1,2,4-triazole derivatives
On nitrogen-atoms formed N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, N3-bridging pattern
Similar.Specific use for triazole class compounds is also manifested by the design of molecular device, and synthesis has different dimension
Metal complex is to complete the vital step of device.
The present invention is i.e. to select Cu (NO3)2With 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-
1,2,4-triazole (L) prepares copper complex [Cu (L) when normal temperature volatilization2(NO3)2] (1).Catalysis experiments proves,
This complex can be applied as the catalyst of phenyl boric acid coupling reaction
1 g phenyl boric acid, 0.2 g Cs is weighed in 25 mL beakers2CO3, 3 mL DMF and 0.1 g catalyst (complex
1), stirring 1 hour under room temperature, TLC monitoring (PE:EA=1:1) reaction is complete, 10 mLCH2Cl220 mL are used again after extracted products
Distilled water washs, organic phase sewage MgSO4Being dried, filtering, precipitation, the thick product obtaining strips post with petroleum ether, obtains
Biphenyl.
Claims (2)
1. application in terms of preparation is as the coupling reaction catalyst of phenyl boric acid for the double triazole copper complex monocrystalline of oxygen ether, its feature
It is that this mono-crystalline structures uses APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha ray, λ=
0.71073 is incident radiation, withω -2θScan mode collects point diffraction, obtains structure cell ginseng through least square refinement
Number, utilizes software to solve single crystal data from difference Fourier electron-density map:
The molecular formula of the double triazole copper complex monocrystalline of described oxygen ether: [Cu (L)2(NO3)2], wherein L=1-(4-(4-(1H-
1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole.
2. application according to claim 1, wherein the method for phenyl boric acid coupling reaction is as follows:
1 g phenyl boric acid, 0.2 g Cs is weighed in 25 mL beakers2CO3, the catalyst complexes monocrystalline of 3 mL DMF and 0.1 g,
Stirring 1 hour under room temperature, TLC monitors, 10 mLCH2Cl2Again with 20 mL distilled water washings after extracted products, organic phase is with anhydrous
MgSO4Being dried, filtering, precipitation, the thick product obtaining strips post with petroleum ether, obtains biphenyl.
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