CN104497021A - Triazole and copper fluoroborate complex with 4-methoxyphenylboronic acid catalyzing effect and preparation method of triazole and copper fluoroborate complex - Google Patents
Triazole and copper fluoroborate complex with 4-methoxyphenylboronic acid catalyzing effect and preparation method of triazole and copper fluoroborate complex Download PDFInfo
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- CN104497021A CN104497021A CN201410769214.5A CN201410769214A CN104497021A CN 104497021 A CN104497021 A CN 104497021A CN 201410769214 A CN201410769214 A CN 201410769214A CN 104497021 A CN104497021 A CN 104497021A
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Abstract
The invention relates to a triazole and copper fluoroborate complex with a 4-methoxyphenylboronic acid catalyzing effect and a preparation method of the triazole and copper fluoroborate complex, and discloses a preparation method of {[Cu(L)] (BF4)2.0.5H2O} (1) (L=4-(3-(4H-1, 2, 4-triazole-4-yl)phenyl)-4H-1, 2, 4-triazole) and a potential application value of {[Cu(L)] (BF4)2.0.5H2O} (1) (L=4-(3-(4H-1, 2, 4-triazole-4-yl)phenyl)-4H-1, 2, 4-triazole) for catalyzing coupled reaction of 4-methoxyphenylboronic acid. The complex is prepared by using a hydrothermal method comprising the step of reacting Cu(BF4)2 and L under a 100-DEG C hydrothermal condition. The invention further discloses application of {[Cu(L)] (BF4)2.0.5H2O} (1) (L=4-(3-(4H-1, 2, 4-triazole-4-yl)phenyl)-4H-1, 2, 4-triazole) as a catalyst for coupled reaction of 4-methoxyphenylboronic 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)] (BF
4)
20.5H
2o} (
1) application of the preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) and the catalyzer aspect as 4-methoxyphenylboronic acid linked 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 catalyzer to develop the organic synthesis of highly selective, 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, polymkeric substance, functional materials, liquid crystal, drug molecule and bioactive compounds.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 bridgingligands 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 mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
The present invention selects Cu (BF
4)
2with 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100
oc hydrothermal condition gets off to prepare copper complex { [Cu (L)] (BF
4)
20.5H
2o} (
1).Catalysis experiments proves, the catalyzer that this title complex can be used as 4-methoxyphenylboronic acid linked reaction is applied.
Summary of the invention
Another object of the present invention is to provide a kind of isophthalic two triazole copper complex { [Cu (L)] (BF
4)
20.5H
2o} (
1) monocrystalline and preparation method thereof.
Current inventor provides following technical scheme for this reason:
Two triazole copper complex { [Cu (L)] (BF of isophthalic
4)
20.5H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) structural motif as shown in Figure 1.
The present invention further discloses two triazole copper complex { [Cu (L)] (BF of isophthalic
4)
20.5H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline, it is characterized in that this single crystal structure 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 unit cell parameters, utilize software to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex
1crystallographic data
Two triazole copper complex { [Cu (L)] (BF of isophthalic of the present invention
4)
20.5H
2o} (
1) preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline, its feature in employing " hydrothermal method ", at CH
3cN and H
2in O, by Cu (BF
4)
2with L ligand 1 00
oreact under C hydrothermal condition, obtain the yellow rhabdolith of applicable X-ray single crystal diffraction.Wherein CH
3cN and H
2the volume ratio of O is 4:6, Cu (BF
4)
2be 1:1 with the mol ratio of L;
The more detailed preparation method of the present invention is as follows:
Two triazole copper complex { [Cu (L)] (BF of a kind of isophthalic
4)
20.5H
2o} (
1) preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline, its feature in employing " hydrothermal method ", at CH
3cN and H
2in O, by Cu (BF
4)
2with L ligand 1 00
oreact under C hydrothermal condition, obtain the yellow rhabdolith of applicable X-ray single crystal diffraction.Wherein CH
3cN and H
2the volume ratio of O is 4:6, Cu (BF
4)
2be 1:1 with the mol ratio of L;
Solvent of the present invention is mixed solvent, CH
3cN and H
2o.
Wherein Cu (BF
4)
2be 1:1 with the mol ratio of L.
The present invention further discloses the effect that the two triazole copper complex of a kind of isophthalic has catalysis 4-methoxyphenylboronic acid linked reaction.
Two triazole copper complex { [Cu (L)] (BF of a kind of isophthalic disclosed by the invention
4)
20.5H
2o} (
1) advantage and disadvantage that has of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-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) { [Cu (L)] (BF prepared by the present invention
4)
20.5H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) production cost is low, method is easy, is applicable to scale operation.
Accompanying drawing explanation
Fig. 1: title complex
1crystalline structure primitive figure;
Fig. 2: title complex
1tomograph;
The nuclear-magnetism figure of Fig. 3: 4,4'-dimethoxy-biphenyl.
Embodiment
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 (BF
4)
2, CH
3cN 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 50 mL, tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, add mphenylenediamine (1 mmol) respectively, two formyl hydrazine (2 mmol), starts and is stirred in 100 DEG C, reacts 12 hours.After reaction terminates, reaction solution is down to room temperature, separates out and precipitate in a large number, by precipitation water and ethyl alcohol recrystallization, yield 86%.Ultimate analysis C
10h
8n
6theoretical value: C, 56.60; H, 3.80; N, 39.60.Experimental value: C, 56.56; H, 3.75; N, 39.56.Mphenylenediamine, the mol ratio of two formyl hydrazine is 1:2.
Embodiment 2
Cu (BF
4)
2with 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) mol ratio of (L) is 1:1;
L (0.0424 g, 0.2 mmol), Cu (BF
4)
2(0.0691 g, 0.2 mmol), H
2o (6 mL), CH
3cN (4 mL), hydro-thermal 100
oc is slowly down to room temperature in tri-days afterwards.The yellow rhabdolith that applicable X-ray single crystal diffraction is analyzed is had after driving still.Productive rate: 35% (calculating based on L).Ultimate analysis (C
10h
9bCuF
4n
6o
0.5) theoretical value (%): C, 32.32; H, 2.44; N, 22.62.Measured value: C, 32.35; H, 2.46; N, 22.69.
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 unit cell parameters, utilize software to solve crystalline structure from difference Fourier electron density map through least-squares refinement, and through Lorentz lorentz and polarizing 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 the three-dimensional structure of title complex is shown in Fig. 2.
Table 1 title complex
1crystallographic data
Embodiment 4
Cu (BF
4)
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 (BF
4)
2with-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) mol ratio be 2:1, then the length of no matter hydro-thermal reaction time, all can not get crystalline compound.Therefore Cu (BF
4)
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 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 catalyzer to develop the organic synthesis of highly selective, 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, polymkeric substance, functional materials, liquid crystal, drug molecule and bioactive compounds.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 bridgingligands 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 mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
The present invention selects Cu (BF
4)
2with 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100
oc hydrothermal condition gets off to prepare copper complex { [Cu (L)] (BF
4)
20.5H
2o} (
1).Catalysis experiments proves, the catalyzer that this title complex can be used as 4-methoxyphenylboronic acid linked reaction is applied.
1 g 4-methoxyphenylboronic acid is taken, 0.2 g Cs in 25 mL beakers
2cO
3, 3 mL DMF and 0.1 g catalyzer (title complex
1), stirred at ambient temperature 1 hour, TLC monitoring (PE:EA=1:1) reacts completely, 10 mL CH
2cl
220 mL distilled water washs are used again, organic phase sewage MgSO after extracted products
4drying, filter, precipitation, the thick product obtained strips post with sherwood oil, obtains 4,4'-dimethoxy-biphenyl.
Claims (4)
1. two triazole copper complex { [Cu (L)] (BF of isophthalic
4)
20.5H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) structural motif as shown in Figure 1.
2. the monocrystalline of copper complex described in claim 1, is characterized in that this single crystal structure 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 unit cell parameters, utilize software to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex
1crystallographic data
。
3. { [Cu (L)] (BF of copper complex described in claim 1
4)
20.5H
2o} (
1) preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole), it is characterized in that adopting it to be adopt hydrothermal method, i.e. Cu (BF
4)
2with 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100
oc hydrothermal condition gets off and prepares this title complex;
Described solvent is mixed solvent is CH
3cN and H
2o; Wherein Cu (BF
4)
2be 1:1 with the mol ratio of 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L).
4. { [Cu (L)] (BF of copper complex described in claim 1
4)
20.5H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) can be used as the application of the coupling reaction catalyst aspect of 4-methoxyphenylboronic acid.
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|---|---|---|---|
| CN201410769214.5A CN104497021B (en) | 2014-12-15 | 2014-12-15 | There is triazole-Tetrafluoroboric acid copper complex of catalysis 4-methoxyphenylboronic acid and preparation method thereof |
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|---|---|---|---|
| CN201410769214.5A CN104497021B (en) | 2014-12-15 | 2014-12-15 | There is triazole-Tetrafluoroboric acid copper complex of catalysis 4-methoxyphenylboronic acid and preparation method thereof |
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| CN104497021B CN104497021B (en) | 2016-10-12 |
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Non-Patent Citations (4)
| Title |
|---|
| BALDEV SINGH ET AL.: "Clay encapsulated Cu(OH)xpromoted homocoupling of arylboronic acids: An efficient and eco-friendly protocol", 《APPLIED CATALYSIS A:GENERAL》, vol. 470, 8 November 2013 (2013-11-08), pages 232 - 238, XP 028669679, DOI: doi:10.1016/j.apcata.2013.10.048 * |
| KASI PITCHUMANI ET AL.: "Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal–organic frameworks", 《GREEN CHEMISTRY》, vol. 16, 24 February 2014 (2014-02-24), pages 2865 - 2875 * |
| N KIRAI ET AL.: "Homocoupling of Arylboronic Acids Catalyzed by 1,10-Phenanthroline-Ligated Copper Complexes in Air", 《EUR. J. ORG. CHEM.》, vol. 12, 31 December 2009 (2009-12-31), pages 1864 - 1867 * |
| SHAO-BIN MIAO ET AL.: "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", 《J CLUST SCI.》, vol. 25, 2 February 2014 (2014-02-02), pages 1137 - 1145 * |
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