CN104447807A - Triazole-cupric tetrafluoroborate complex capable of catalyzing phenylboronic acid and preparation method of complex - Google Patents

Triazole-cupric tetrafluoroborate complex capable of catalyzing phenylboronic acid and preparation method of complex Download PDF

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CN104447807A
CN104447807A CN201410767588.3A CN201410767588A CN104447807A CN 104447807 A CN104447807 A CN 104447807A CN 201410767588 A CN201410767588 A CN 201410767588A CN 104447807 A CN104447807 A CN 104447807A
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triazole
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copper complex
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CN104447807B (en
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王英
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Tianjin Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation 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
    • C07C1/321—Preparation 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/12—Polycyclic non-condensed hydrocarbons
    • C07C15/14—Polycyclic non-condensed hydrocarbons all phenyl groups being directly linked
    • 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
    • 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
    • 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
    • B01J2531/02—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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Abstract

The invention 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 potential application value for catalyzing coupled reaction of phenylboronic acid. According to the preparation method, the complex is prepared by using a hydrothermal method, i.e., reaction on Cu(BF4)2 and L is carried out under a hydrothermal condition at 100 DEG C. The invention further discloses an 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 phenylboronic 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 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 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 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 phenylo boric 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.
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 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 phenylo boric acid linked reaction is applied.
    
1 g phenylo boric 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 mLCH 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 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 phenylo boric acid.
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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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103086988A (en) * 2013-02-21 2013-05-08 天津师范大学 Phenyl bistriazole compound, and preparation method and application thereof
CN104370944A (en) * 2014-11-10 2015-02-25 天津师范大学 M-benzene ditriazole Cu-boric acid complex as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103086988A (en) * 2013-02-21 2013-05-08 天津师范大学 Phenyl bistriazole compound, and preparation method and application thereof
CN104370944A (en) * 2014-11-10 2015-02-25 天津师范大学 M-benzene ditriazole Cu-boric acid complex as well as preparation method and application thereof

Non-Patent Citations (2)

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PILLAIYAR P ET AL: ""Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal–organic frameworks"", 《GREEN CHEM》 *
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》 *

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