CN104557985A - Oxygen ether dual-triazole copper complex capable of catalyzing p-fluorophenylboronic acid and preparation method of oxygen ether dual-triazole copper complex - Google Patents
Oxygen ether dual-triazole copper complex capable of catalyzing p-fluorophenylboronic acid and preparation method of oxygen ether dual-triazole copper complex Download PDFInfo
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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
- B01J31/18—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
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- 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- 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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- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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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Abstract
The invention discloses an oxygen ether dual-triazole copper complex capable of catalyzing p-fluorophenylboronic acid and a preparation method of the oxygen ether dual-triazole copper complex. The complex is prepared from Cu(NO3)2 and L by adopting a 'normal temperature volatilization method' under normal temperature stirring and volatilization conditions. The invention further discloses application of (Cu(L)2(NO3)2)(1)(L=1-(4-(4-(1H-1, 2, 4-triazole-1-yl) phenoxy) phenyl)-1H-1, 2, 4-triazole) as a coupling reaction catalyst of p-fluorophenylboronic 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)
2(NO
3)
2] (
1) preparation method of (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-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 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 (NO
3)
2under normal temperature condition, copper complex [Cu (L) is prepared with 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L)
2(NO
3)
2] (
1).Catalysis experiments proves, this complex can be used as to be applied the catalyst of fluorobenzoic boric 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)
2(NO
3)
2] (
1) monocrystalline and preparation method thereof.
Current inventor provides following technical scheme for this reason:
The two triazole copper complex [Cu (L) of oxygen ether
2(NO
3)
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 two triazole copper complex [Cu (L) of oxygen ether
2(NO
3)
2] (
1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-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
The two triazole copper complex [Cu (L) of oxygen ether of the present invention
2(NO
3)
2] (
1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) preparation method of monocrystalline, its feature is adopt " normal temperature volatility process ", i.e. Cu (NO at it
3)
2get off to obtain the yellow rhabdolith of applicable X-ray single crystal diffraction with L stirring at normal temperature volatilization condition.Wherein CH
3oH and H
2the volume ratio of O is 4:6, Cu (NO
3)
2be 1:1 with the mol ratio of L;
The more detailed preparation method of the present invention is as follows:
The two triazole copper complex [Cu (L) of a kind of oxygen ether
2(NO
3)
2] (
1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) preparation method of monocrystalline, its feature adopts " normal temperature volatility process ", i.e. Cu (NO at it
3)
2get off to obtain the yellow rhabdolith of applicable X-ray single crystal diffraction with L stirring at normal temperature volatilization condition.Wherein CH
3oH and H
2the volume ratio of O is 4:6, Cu (NO
3)
2be 1:1 with the mol ratio of L;
Solvent of the present invention is mixed solvent, CH
3oH and H
2o.
Wherein Cu (NO
3)
2be 1:1 with the mol ratio of L.
The present invention further discloses the two triazole copper complex of a kind of oxygen ether and there is the effect of catalysis to fluorobenzoic boric acid coupling reaction.
The two triazole copper complex [Cu (L) of a kind of oxygen ether disclosed by the invention
2(NO
3)
2] (
1) advantage and disadvantage that has of (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-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) [the Cu (L) prepared by the present invention
2(NO
3)
2] (
1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-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
1one-dimensional catenary structure figure.
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, 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.Wherein Cu (NO
3)
2, CH
3oH 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, the preparation method of 4-triazole, its feature employing " one kettle way ", in DMF polar solvent, by 1,1,2,2-tetra-(4-bromophenyl) ethene, triazole, this organic compound prepared in a heated condition by potash and cupric oxide; Wherein 4,4 '-dibromodiphenyl ether: triazole: potash: the mol ratio of cupric oxide is 2:10:30:1;
Reaction temperature 150 DEG C, 18 hours reaction time.
Embodiment 2
Cu (NO
3)
2be 1:1 with the mol ratio of 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L);
L (0.0304 g, 0.1 mmol) and Cu (NO
3)
2(0.0242 g, 0.1 mmol) is at H
2o (6 mL) and CH
3in the mixed solvent of OH (4 mL), stirring at normal temperature was filtered after half an hour, the yellow rhabdolith that filtrate normal temperature volatilization X-ray single crystal diffraction is analyzed.Productive rate: 45% (calculating based on L).Elementary analysis (C
32h
24cuN
14o
8) theoretical value (%): C, 48.27; H, 3.04; N, 24.63.Measured value: C, 48.25; H, 3.16; N, 24.66.
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 one-dimensional catenary structure is shown in Fig. 2.
Table 1. complex
1crystallographic data
Embodiment 4
Cu (NO
3)
2be 1:1 with 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L) mol ratio;
We also attempted other ratios, such as Cu (NO
3)
2be 2:1 with the mol ratio of 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L), then the length of no matter hydro-thermal reaction time, all can not get crystalline compound.Therefore Cu (NO
3)
2be 1:1 with the mol ratio of 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L) be optimum response proportioning.
Embodiment 5
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 (NO
3)
2under normal temperature volatilization condition, copper complex [Cu (L) is prepared with 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L)
2(NO
3)
2] (
1).Catalysis experiments proves, this complex can be used as to be applied the catalyst of fluorobenzoic boric acid coupling reaction.
1 g is taken to fluorobenzoic boric 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'-DfBP.
Claims (4)
1. the two triazole copper complex [Cu (L) of oxygen ether
2(NO
3)
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 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. [the Cu (L) of copper complex described in claim 1
2(NO
3)
2] (
1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) preparation method, it is characterized in that it be adopt " normal temperature volatility process ", i.e. Cu (NO
3)
2get off to prepare this complex with L stirring at normal temperature volatilization condition;
Described solvent is mixed solvent is CH
3oH and H
2o; Wherein Cu (NO
3)
2be 1:1 with the mol ratio of 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L).
4. the two triazole copper complex [Cu (L) of oxygen ether described in claim 1
2(NO
3)
2] (
1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) can be used as the application of the coupling reaction catalyst aspect to fluorobenzoic boric acid.
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| CN105732668A (en) * | 2016-04-25 | 2016-07-06 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole copper mixed complex single crystal and application |
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|---|---|---|---|---|
| CN103772305A (en) * | 2014-01-14 | 2014-05-07 | 天津师范大学 | Oxyether triazole compound, and preparation method and application thereof |
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| CN103772305A (en) * | 2014-01-14 | 2014-05-07 | 天津师范大学 | Oxyether triazole compound, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| KASI PITCHUMANI ET AL.: "Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal–organic frameworks", 《GREEN CHEM.》 * |
| N KIRAI ET AL.: "Homocoupling of Arylboronic Acids Catalyzed by 1,10-Phenanthroline-Ligated Copper Complexes in Air", 《EUR. J. ORG. CHEM.》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105732668A (en) * | 2016-04-25 | 2016-07-06 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole copper mixed complex single crystal and application |
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