CN104447807B - Triazole-Tetrafluoroboric acid copper complex with catalysis phenylo boric acid and preparation method thereof - Google Patents

Triazole-Tetrafluoroboric acid copper complex with catalysis phenylo boric acid and preparation method thereof Download PDF

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CN104447807B
CN104447807B CN201410767588.3A CN201410767588A CN104447807B CN 104447807 B CN104447807 B CN 104447807B CN 201410767588 A CN201410767588 A CN 201410767588A CN 104447807 B CN104447807 B CN 104447807B
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triazole
boric acid
phenylo boric
copper complex
isophthalic
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CN104447807A (en
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王英
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Tianjin Normal University
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    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts 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
    • B01J31/1805Catalysts 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
    • B01J31/181Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815Cyclic 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/12Polycyclic non-condensed hydrocarbons
    • C07C15/14Polycyclic non-condensed hydrocarbons all phenyl groups being directly linked
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40Substitution 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
    • B01J2231/42Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238Complexes 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16Copper
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    • C07ORGANIC CHEMISTRY
    • C07BGENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07B2200/13Crystalline forms, e.g. polymorphs

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Abstract

The invention discloses one { [Cu (L)] (BF 4) 20.5H 2o} (<b>1</bGreatT.Gr eaT.GT) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) preparation method and as catalysis phenylo boric acid linked reaction, there is potential using value.It adopts " hydrothermal method ", i.e. Cu (BF 4) 2with L 100 oc hydrothermal condition gets off and prepares this title complex.The present invention further discloses { [Cu (L)] (BF 4) 20.5H 2o} (<b>1</bGreatT.Gr eaT.GT) (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 phenylo boric acid.

Description

Triazole-Tetrafluoroboric acid copper complex with catalysis phenylo boric acid and preparation method thereof
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 2the application of the preparation method of O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) and the catalyzer aspect as phenylo boric 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 phenylo boric 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 2the structural motif of O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) 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 APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, point diffraction is collected with ω-2 θ scan mode, obtain unit cell parameters through least-squares refinement, utilize software to solve single crystal data from difference Fourier electron density map:
The crystallographic data of table 1. title complex 1
Two triazole copper complex { [Cu (L)] (BF of isophthalic of the present invention 4) 20.5H 2the preparation method of O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline, its feature 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 2the preparation method of O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline, its feature 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 phenylo boric acid linked reaction.
Two triazole copper complex { [Cu (L)] (BF of a kind of isophthalic disclosed by the invention 4) 20.5H 2the advantage and disadvantage that O} (1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline has 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, and method is easy, is applicable to scale operation.
Accompanying drawing explanation
Fig. 1: the crystalline structure primitive figure of title complex 1;
Fig. 2: the tomograph of title complex 1.
Fig. 3: the nuclear-magnetism figure of 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 50mL tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, add mphenylenediamine (1mmol) respectively, two formyl hydrazine (2mmol), 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 (0.0424g, 0.2mmol), Cu (BF 4) 2(0.0691g, 0.2mmol), H 2o (6mL), CH 3cN (4mL), 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 APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, point diffraction is collected with ω-2 θ scan mode, unit cell parameters is obtained through least-squares refinement, software is utilized to solve crystalline structure from difference Fourier electron density map, 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.
The crystallographic data of table 1. title complex 1
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 phenylo boric acid linked reaction is applied.
1g phenylo boric acid is taken, 0.2gCs in 25mL beaker 2cO 3, 3mLDMF and 0.1g catalyzer (title complex 1), stirred at ambient temperature 1 hour, TLC monitoring (PE:EA=1:1) reacts completely, 10mLCH 2cl 220mL distilled water wash is used again, organic phase sewage MgSO after extracted products 4drying, filter, precipitation, the thick product obtained strips post with sherwood oil, obtains biphenyl.

Claims (2)

1. the application in the coupling of phenylo boric acid autoxidation prepared by the two triazole copper complex monocrystalline of isophthalic, it is characterized in that: the two triazole copper complex monocrystalline of this isophthalic adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray, λ=0.71073 is incident radiation, point diffraction is collected with ω-2 θ scan mode, obtain unit cell parameters through least-squares refinement, utilize software to solve single crystal data from difference Fourier electron density map:
Wherein structure [Cu (L)] (BF of the two triazole copper complex of isophthalic 4) 20.5H 2o, wherein L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole.
2. application according to claim 1, the method wherein preparing the coupling of phenylo boric acid autoxidation is as follows:
Phenylo boric acid biphenyl
1g phenylo boric acid is taken, 0.2gCs in 25mL beaker 2cO 3, 3mLDMF and 0.1g catalytic complex monocrystalline, stirred at ambient temperature 1 hour, TLC monitors, 10mLCH 2cl 220mL distilled water wash is used again, the anhydrous MgSO of organic phase after extracted products 4drying, filter, precipitation, the thick product obtained strips post with sherwood oil, obtains biphenyl.
CN201410767588.3A 2014-12-15 2014-12-15 Triazole-Tetrafluoroboric acid copper complex with catalysis phenylo boric acid and preparation method thereof Expired - Fee Related CN104447807B (en)

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