CN104497020B - There is triazole-cupric perchlorate coordination compound of catalysis 4-pyridine phenylboric acid and preparation method thereof - Google Patents
There is triazole-cupric perchlorate coordination compound of catalysis 4-pyridine phenylboric acid and preparation method thereof Download PDFInfo
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- CN104497020B CN104497020B CN201410768491.4A CN201410768491A CN104497020B CN 104497020 B CN104497020 B CN 104497020B CN 201410768491 A CN201410768491 A CN 201410768491A CN 104497020 B CN104497020 B CN 104497020B
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- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/08—Copper compounds
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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
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- 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
- C07D213/127—Preparation from compounds containing pyridine rings
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- 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
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- 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
Abstract
The invention discloses one { [Cu (L)] (ClO4)·0.25H2The preparation method of O} (1) (L=4 (3 (4H 1,2,4 triazole 4 base) phenyl) 4H 1,2,4 triazole).It is to use " hydro-thermal method ", i.e. Cu (ClO4)2Under 100 DEG C of hydrothermal conditions, this coordination compound is prepared with L.The present invention further discloses copper complex { [Cu (L)] (ClO4)·0.25H2O} (1) (L=4 (3 (4H 1,2,4 triazole 4 base) phenyl) 4H 1,2,4 triazole) is as the application in terms of the coupling reaction catalyst of 4 pyridine phenylboric acids.
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 subsidizes (TD12-5038).
Technical field
The invention belongs to Inorganic synthese technical field, relate to copper complex { [Cu (L)] (ClO4)·0.25H2O} (1) (L
=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) preparation method and even as 4-pyridine phenylboric acid
Application in terms of the catalyst of connection reaction.
Background technology
A research always active field of high selectivity is carried out with transition metal complex catalysis.With commonly
Synthesizing mean is difficult to the reaction realized, and busy use transition metal complex can a step complete in a mild condition.Therefore, adopt
Make catalyst with metal complex and develop the organic synthesis of high selectivity, high conversion, be the most interesting
Problem.In organic synthesis, general conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex demonstrates many
Sample catalysis.Palladium catalysed cross coupling reaction kind is a lot, and these reactions are at synthesis of natural product, polymer, functional material, liquid
Crystalline substance, drug molecule and bioactive compound all have been widely used.But palladium catalyst is relatively costly, if can be with cheap
Copper complex replaces expensive palladium catalyst, it is achieved the process of reaction, is possible not only to cost-effective, and is expected to industry metaplasia
Produce.
1,2,4-triazole and derivant thereof have the coordination feature of pyrazoles and imidazoles concurrently, are that the bridging that coordination ability is stronger is joined
Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound the most.These parts can be former with the nitrogen on 1,2
Son forms N1, N2-bridging pattern with metallic ion coordination, can be by 2,4 for 4 unsubstituted 1,2,4-triazole derivatives
On nitrogen-atoms formed N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, N3-bridging pattern
Similar.Specific use for triazole class compounds is also manifested by the design of molecular device, and synthesis has different dimension
Metal complex has been the vital step of device.
The present invention is i.e. to select Cu (ClO4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole
(L) 100oC hydrothermal condition gets off to prepare copper complex { [Cu (L)] (ClO4)·0.25H2O} (1).Catalysis experiments proves,
This coordination compound can be applied as the catalyst of 4-pyridine phenylboric acid coupling reaction.
Summary of the invention
Offer double triazole copper complex { [Cu (L)] (ClO of a kind of isophthalic is provided4)·
0.25H2O} (1) monocrystalline and preparation method thereof.
Following technical scheme is current inventor provides for this:
Double triazole copper complex { [Cu (L)] (ClO of isophthalic4)·0.25H2O} (1) (L=4-(3-(4H-1,2,4-tri-
Azoles-4-base) phenyl)-4H-1,2,4-triazole) and structural motif as shown in Figure 1；L=4-(3-(4H-1,2,4-triazole-4-yl)
Phenyl)-4H-1,2,4-triazole；
The present invention further discloses double triazole copper complex { [Cu (L)] (ClO of isophthalic4)·0.25H2O} (1) (L =
4-(3-(4H-1,2,4-triazole-4-yls) phenyl)-4H-1,2,4-triazoles) monocrystalline, it is characterised in that this mono-crystalline structures uses
APEX II CCD single crystal diffractometer, use is incident radiation through graphite monochromatised Mok alpha ray (λ=0.71073),
Collect point diffraction with ω-2 θ scan mode, obtain cell parameter through least square refinement, from difference Fourier electron density
Desire to make money or profit and solve single crystal data with software:
The crystallographic data of table 1. coordination compound 1
Double triazole copper complex { [Cu (L)] (ClO of isophthalic of the present invention4)·0.25H2O} (1) (L = 4-(3-
(4H-1,2,4-triazole-4-yls) phenyl)-4H-1,2,4-triazoles) preparation method of monocrystalline, its feature is using " hydro-thermal method ",
At CH3CN and H2In O, by Cu (ClO4)2With L ligand 1 00oReact under C hydrothermal condition, obtain being suitable for X-ray single crystal diffraction
Yellow rhabdolith.Wherein CH3CN and H2The volume ratio of O is 4:6, Cu (ClO4)2It is 1:1 with the mol ratio of L；
The more detailed preparation method of the present invention is as follows:
Double triazole copper complex { [Cu (L)] (ClO of a kind of isophthalic4)·0.25H2O} (1) (L = 4-(3-(4H-1,2,
4-triazole-4-yl) phenyl)-4H-1,2,4-triazoles) preparation method of monocrystalline, its feature is using " hydro-thermal method ", at CH3CN and
H2In O, by Cu (ClO4)2With L ligand 1 00oReacting under C hydrothermal condition, the yellow obtaining being suitable for X-ray single crystal diffraction is bar-shaped
Crystal.Wherein CH3CN and H2The volume ratio of O is 4:6, Cu (ClO4)2It is 1:1 with the mol ratio of L；
Solvent of the present invention is mixed solvent, CH3CN and H2O。
Wherein Cu (ClO4)2It is 1:1 with the mol ratio of L.
The present invention further discloses copper complex { [Cu (L)] (ClO4)·0.25H2O} (1) (L = 4-(3-(4H-
1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) as the application in terms of 4-pyridine phenylboric acid coupling reaction catalyst.
Double triazole copper complex { [Cu (L)] (ClO of a kind of isophthalic disclosed by the invention4)·0.25H2O}(1) (L = 4-
(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline have the advantage that and feature be:
(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)] (ClO prepared by the present invention4)·0.25H2O}n(1) (L=4-(3-(4H-1,2,4-tri-
Azoles-4-base) phenyl)-4H-1,2,4-triazoles) production cost is low, and method is easy, is suitable for large-scale production.
Accompanying drawing explanation
The crystal structure primitive figure of Fig. 1: coordination compound 1；
The tomograph of Fig. 2: coordination compound 1；
The nuclear-magnetism figure of Fig. 3: 4,4'-bipyridyl.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, and embodiment is only explanatory, is in no way intended to it
Limit the scope of the present invention by any way.All of raw material is all to buy from chemical reagents corporation both domestic and external, does not has
Through continuation purification but directly use.Raw materials used 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
It is separately added into m-diaminobenzene. (1 in equipped with 50 mL three neck round bottom flasks of magneton, reflux condenser and thermometer
Mmol), double formylhydrazines (2 mmol), start and stir at 160 DEG C, react 12 hours.After reaction terminates, reactant liquor is down to room
Temperature, separates out a large amount of precipitation, by precipitation water and ethyl alcohol recrystallization, yield 86%.Elementary analysis C10H8N6Theoretical value: C, 56.60；
H, 3.80；N, 39.60.Experiment value: C, 56.56；H, 3.75；N, 39.56.M-diaminobenzene., the mol ratio of double formylhydrazines is 1:2.
Embodiment 2
Cu(ClO4)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 (ClO4)2(0.0691 g, 0.2 mmol), H2O (6 mL), CH3CN
(4 mL), hydro-thermal 100oC was slowly dropped to room temperature after tri-days.The yellow having applicable X-ray single crystal diffraction to analyze after driving still is bar-shaped
Crystal.Productivity: 35% (calculating based on L).Elementary analysis (C10H8.5ClCuN6O4.25) theoretical value (%): C, 30.67；H, 2.03；
N, 19.51.Measured value: C, 30.63；H, 2.06；N, 19.59.We also attempted other ratios, such as Cu (ClO4)2With L's
Mol ratio is 2:1, and the most no matter the length of hydro-thermal reaction time, all can not get crystalline compound.Therefore Cu (ClO4)2With L mole
Ratio is optimum response proportioning for 1:1.
Embodiment 3
Crystal structure determination uses APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha ray (λ=
0.71073) it is incident radiation, collects point diffraction with ω-2 θ scan mode, obtain structure cell ginseng through least square refinement
Number, utilizes software to solve crystal structure from difference Fourier electron density map, and through Lorentz lorentz and polarity effect correction.All of
H atom is synthesized by difference Fourier and determines through preferable position calculation.Detailed axonometry data are shown in Table 1.Structural motif is shown in
Fig. 1, the three dimensional structure of coordination compound is shown in Fig. 2.
The crystallographic data of table 1 coordination compound 1
Embodiment 4
A research always active field of high selectivity is carried out with transition metal complex catalysis.With commonly
Synthesizing mean is difficult to the reaction realized, and busy use transition metal complex can a step complete in a mild condition.Therefore, adopt
Make catalyst with metal complex and develop the organic synthesis of high selectivity, high conversion, be the most interesting
Problem.In organic synthesis, general conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex demonstrates many
Sample catalysis.Palladium catalysed cross coupling reaction kind is a lot, and these reactions are at synthesis of natural product, polymer, functional material, liquid
Crystalline substance, drug molecule and bioactive compound all have been widely used.But palladium catalyst is relatively costly, if can be with cheap
Copper complex replaces expensive palladium catalyst, it is achieved the process of reaction, is possible not only to cost-effective, and is expected to industry metaplasia
Produce.
1,2,4-triazole and derivant thereof have the coordination feature of pyrazoles and imidazoles concurrently, are that the bridging that coordination ability is stronger is joined
Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound the most.These parts can be former with the nitrogen on 1,2
Son forms N1, N2-bridging pattern with metallic ion coordination, can be by 2,4 for 4 unsubstituted 1,2,4-triazole derivatives
On nitrogen-atoms formed N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, N3-bridging pattern
Similar.Specific use for triazole class compounds is also manifested by the design of molecular device, and synthesis has different dimension
Metal complex has been the vital step of device.
The present invention is i.e. to select Cu (ClO4)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole
(L) 100oC hydrothermal condition gets off to prepare copper complex { [Cu (L)] (ClO4)·0.25H2O} (1).Catalysis experiments proves,
This coordination compound can be applied as the catalyst of 4-pyridine phenylboric acid coupling reaction.
1 g 4-pyridine phenylboric acid, 0.2 g Cs is weighed in 25 mL beakers2CO3, 3 mL DMF and 0.1 g catalyst (coordinate
Thing 1), to stir 1 hour under room temperature, TLC monitoring (PE:EA=1:1) reaction is complete, 10 mL CH2Cl2Again with 20 after extracted products
ML distilled water wash, organic facies sewage MgSO4Being dried, filter, precipitation, the thick product obtained strips post with petroleum ether,
To 4,4'-bipyridyl.
Claims (1)
1. the double triazole copper complex monocrystalline of isophthalic in preparation as the application in terms of the catalyst of 4-pyridine phenylboric acid coupling reaction,
The chemical formula of the double triazole copper complex monocrystalline of described isophthalic: [Cu (L)] (ClO4)·0.25H2O；L = 4-(3-(4H-1,2,
4-triazole-4-yl) phenyl)-4H-1,2,4-triazoles, this mono-crystalline structures uses APEX II CCD single crystal diffractometer, uses and passes through
Graphite monochromatised Mok alpha ray, λ=0.71073 is incident radiation, collects point diffraction with ω-2 θ scan mode, through
Little square law correction obtains cell parameter, utilizes software to solve single crystal data from difference Fourier electron density map:
。
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| CN104356147A (en) * | 2014-11-10 | 2015-02-18 | 天津师范大学 | Triazole Cu-hypochlorite complex with potential ferroelectric functions and preparation method thereof |
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| CN104356147A (en) * | 2014-11-10 | 2015-02-18 | 天津师范大学 | Triazole Cu-hypochlorite complex with potential ferroelectric functions and preparation method thereof |
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| Title |
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| Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal-organic frameworks;Pillaiyar Puthiaraj, et al.;《Green Chem.》;20140224;第16卷;2865-2875 * |
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