CN104860965A - Triazole-copper(II) trifluoromethanesulfonate complex for catalysis of 4-pyridine phenylboronic acid and preparation method therefor - Google Patents

Triazole-copper(II) trifluoromethanesulfonate complex for catalysis of 4-pyridine phenylboronic acid and preparation method therefor Download PDF

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CN104860965A
CN104860965A CN201410769420.6A CN201410769420A CN104860965A CN 104860965 A CN104860965 A CN 104860965A CN 201410769420 A CN201410769420 A CN 201410769420A CN 104860965 A CN104860965 A CN 104860965A
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triazole
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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
    • C07F1/08—Copper compounds
    • 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
    • B01J31/184—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine mixed aromatic/aliphatic ring systems, e.g. indoline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper

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Abstract

The invention discloses a preparation method for {[Cu(L)](CF3SO3).0.33H2O} (1) (L is 4-(3-(4H-1,2,4- triazolyl-4)-phenyl)-4H-1,2,4-triazole) and potential application values for catalysis of a coupling reaction of 4-pyridine phenylboronic acid. The hydrothermal method is employed, namely, Cu(CF3SO3)2 and L are employed for preparation of the complex under a hydro-thermal condition of 100 DEG C. The invention further discloses applications of the copper complex {[Cu(L)](CF3SO3).0.33H2O} (1) (L is 4-(3-(4H-1,2,4- triazolyl-4)-phenyl)-4H-1,2,4-triazole) as a catalyst for catalysis of a coupling reaction of 4-pyridine phenylboronic acid.

Description

Triazole-copper triflate title complex with catalysis 4-pyridine 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)] (CF 3sO 3) 0.33H 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-pyridine 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 (CF 3sO 3) 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)] (CF 3sO 3) 0.33H 2o} ( 1).Catalysis experiments proves, the catalyzer that this title complex can be used as 4-pyridine 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)] (CF 3sO 3) 0.33H 2o} ( 1) monocrystalline and preparation method thereof.
Current inventor provides following technical scheme for this reason:
Two triazole copper complex { [Cu (L)] (CF of isophthalic 3sO 3) 0.33H 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)] (CF of isophthalic 3sO 3) 0.33H 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)] (CF of isophthalic of the present invention 3sO 3) 0.33H 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 (CF 3sO 3) 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 (CF 3sO 3) 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)] (CF of a kind of isophthalic 3sO 3) 0.33H 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 (CF 3sO 3) 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 (CF 3sO 3) 2be 1:1 with the mol ratio of L;
Solvent of the present invention is mixed solvent, CH 3cN and H 2o.Wherein Cu (CF 3sO 3) 2be 1:1 with the mol ratio of L.
The present invention further discloses copper complex { [Cu (L)] (CF 3sO 3) 0.33H 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 catalyzer aspect of 4-pyridine phenylo boric acid linked reaction.
Two triazole copper complex { [Cu (L)] (CF of a kind of isophthalic disclosed by the invention 3sO 3) 0.33H 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)] (CF prepared by the present invention 3sO 3) 0.33H 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'-dipyridyl.
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.
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 160 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 (CF 3sO 3) 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 (CF 3sO 3) 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 33h 26cu 3f 9n 18o 10s 3) theoretical value (%): C, 30.67; H, 2.03; N, 19.51.Measured value: C, 30.69; H, 2.06; N, 19.59.
We also attempted other ratios, such as Cu (CF 3sO 3) 2be 2:1 with the mol ratio of L, then the length of no matter hydro-thermal reaction time, all can not get crystalline compound.Therefore Cu (CF 3sO 3) 2be 1:1 with the mol ratio of L be optimum response proportioning.
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
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 (CF 3sO 3) 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)] (CF 3sO 3) 0.33H 2o} ( 1).Catalysis experiments proves, the catalyzer that this title complex can be used as 4-pyridine phenylo boric acid linked reaction is applied.
1.1 g 4-pyridine phenylo boric acids are 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'-dipyridyl.

Claims (4)

1. two triazole copper complex { [Cu (L)] (CF of isophthalic 3sO 3) 0.33H 2o} ( 1) structural motif of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole).
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)] (CF of copper complex described in claim 1 3sO 3) 0.33H 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 (CF 3sO 3) 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;
L
Described solvent is mixed solvent is CH 3cN and H 2o;
Wherein Cu (CF 3sO 3) 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)] (CF of copper complex described in claim 1 3sO 3) 0.33H 2o} ( 1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) as the application of the coupling reaction catalyst aspect of 4-pyridine phenylo boric acid.
CN201410769420.6A 2014-12-15 2014-12-15 Triazole-copper triflate coordination compound with catalysis 4-pyridine phenylboric acid and preparation method thereof Expired - Fee Related CN104860965B (en)

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Citations (1)

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CN104447804A (en) * 2014-11-10 2015-03-25 天津师范大学 M-benzene bitriazole Cu-trifluoromethanesulfonic acid complex as well as preparation method and application thereof

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