CN104557986B - Have and be catalyzed triazole-copper triflate coordination compound to fluorobenzoic boric acid and preparation method thereof - Google Patents
Have and be catalyzed triazole-copper triflate coordination compound to fluorobenzoic boric acid and preparation method thereof Download PDFInfo
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- CN104557986B CN104557986B CN201410769197.5A CN201410769197A CN104557986B CN 104557986 B CN104557986 B CN 104557986B CN 201410769197 A CN201410769197 A CN 201410769197A CN 104557986 B CN104557986 B CN 104557986B
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- triazole
- boric acid
- fluorobenzoic boric
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000004327 boric acid Substances 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 title abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 9
- ZIJDTDSIVOVKGW-UHFFFAOYSA-L copper 2H-triazole trifluoromethanesulfonate Chemical compound FC(S(=O)(=O)[O-])(F)F.[Cu+2].N1N=NC=C1.FC(S(=O)(=O)[O-])(F)F ZIJDTDSIVOVKGW-UHFFFAOYSA-L 0.000 title description 2
- 239000010949 copper Substances 0.000 claims abstract description 28
- -1 triazole copper triflate Chemical class 0.000 claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000005260 alpha ray Effects 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 150000004699 copper complex Chemical class 0.000 abstract description 7
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 229910052763 palladium Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- HVMMGTLUNJNHFE-UHFFFAOYSA-N 4-[3-(1,2,4-triazol-4-yl)phenyl]-1,2,4-triazole Chemical compound N=1N=CN(C1)C=1C=C(C=CC1)N1C=NN=C1 HVMMGTLUNJNHFE-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 230000015689 metaplastic ossification Effects 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
Classifications
-
- 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
- B01J31/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of have be catalyzed triazole copper triflate coordination compound of fluorobenzoic boric acid and preparation method thereof.It is to use " hydro-thermal method ", i.e. Cu (CF3SO3)2With L 100oC hydrothermal condition gets off to prepare this coordination compound.The present invention further discloses copper complex { [Cu (L)] (CF3SO3)·0.33H2O} (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 to fluorobenzoic boric 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 subsidizes (TD12-5038).
Technical field
The invention belongs to Inorganic synthese technical field, relate to copper complex { [Cu (L)] (CF3SO3)·0.33H2O} (1)
The preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) and conduct are to fluorobenzoic boric acid
Application in terms of the catalyst of coupling 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 (CF3SO3)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-three
Azoles (L) is 100oC hydrothermal condition gets off to prepare copper complex { [Cu (L)] (CF3SO3)·0.33H2O} (1).Catalysis experiments is demonstrate,proved
Bright, this coordination compound can be applied as to the catalyst of fluorobenzoic boric acid coupling reaction.
Summary of the invention
Offer double triazole copper complex { [Cu (L)] (CF of a kind of isophthalic is provided3SO3)·
0.33H2O} (1) monocrystalline and preparation method thereof.
Following technical scheme is current inventor provides for this:
Double triazole copper complex { [Cu (L)] (CF of isophthalic3SO3)·0.33H2O} (1) (L = 4-(3-(4H-1,2,4-
Triazole-4-yl) 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)] (CF of isophthalic3SO3)·0.33H2O} (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)] (CF of isophthalic of the present invention3SO3)·0.33H2O} (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 (CF3SO3)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 (CF3SO3)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)] (CF of a kind of isophthalic3SO3)·0.33H2O} (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 (CF3SO3)2With L ligand 1 00oReact under C hydrothermal condition, obtain being suitable for the yellow rod of X-ray single crystal diffraction
Shape crystal.Wherein CH3CN and H2The volume ratio of O is 4:6, Cu (CF3SO3)2It is 1:1 with the mol ratio of L；
Solvent of the present invention is mixed solvent, CH3CN and H2O.Wherein Cu (CF3SO3)2It is 1:1 with the mol ratio of L.
The present invention further discloses copper complex { [Cu (L)] (CF3SO3)·0.33H2O} (1) (L = 4-(3-
(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) can be as the catalyst to fluorobenzoic boric acid coupling reaction.
Double triazole copper complex { [Cu (L)] (CF of a kind of isophthalic disclosed by the invention3SO3)·0.33H2O} (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)] (CF prepared by the present invention3SO3)·0.33H2O} (1) (L = 4-(3-(4H-1,2,4-
Triazole-4-yl) 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'-DfBP.
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 such as: anthracene nucleus etc. are all to enter from chemical reagents corporation both domestic and external
Row is bought, and through continuation purification but does not directly use.
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 100 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(CF3SO3)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) mol ratio of (L)
For 1:1；
L (0.0424 g, 0.2 mmol), Cu (CF3SO3)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 that applicable X-ray single crystal diffraction is analyzed is had after driving still
Rhabdolith.Productivity: 35% (calculating based on L).Elementary analysis (C33H26Cu3F9N18O10S3) 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 (CF3SO3)2It is 2:1 with the mol ratio of L, the most no matter during hydro-thermal reaction
Between length, all can not get crystalline compound.Therefore Cu (CF3SO3)2With the mol ratio of L be 2:1 be optimum response proportioning.
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 (CF3SO3)2With 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-three
Azoles (L) is 100oC hydrothermal condition gets off to prepare copper complex { [Cu (L)] (CF3SO3)·0.33H2O} (1).Catalysis experiments is demonstrate,proved
Bright, this coordination compound can be applied as to the catalyst of fluorobenzoic boric acid coupling reaction.
1 g is weighed to fluorobenzoic boric acid, 0.2 g Cs 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'-DfBP.
Claims (2)
1. the double triazole copper complex monocrystalline of isophthalic is as the application in terms of the coupling reaction catalyst to fluorobenzoic boric acid, its feature
It is that this mono-crystalline structures uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, λ=
0.71073 is incident radiation, collects point diffraction with ω-2 θ scan mode, obtains cell parameter through least square refinement,
Software is utilized to solve single crystal data from difference Fourier electron density map:
The wherein structure of the double triazole copper complex monocrystalline of isophthalic: [Cu (L)] (CF3SO3)·0.33H2O, L=4-(3-(4H-1,
2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole.
2. the application described in claim 1, wherein uses this complex monocrystal to carry out the method for coupling reaction as follows:
To fluorobenzoic boric acid 4,4'-DfBP
1 g is weighed to fluorobenzoic boric acid, 0.2 g Cs in 25 mL beakers2CO3, 3 mL DMF and 0.1 g catalyst complexes list
Crystalline substance, stirs 1 hour under room temperature, and TLC monitoring reaction is complete, 10 mL CH2Cl2Again with 20 mL distilled water washs after extracted products,
The anhydrous MgSO of organic facies4Being dried, filter, precipitation, the thick product obtained strips post with petroleum ether, obtains 4, and 4'-difluoro joins
Benzene.
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|---|---|---|---|
| CN201410769197.5A CN104557986B (en) | 2014-12-15 | 2014-12-15 | Have and be catalyzed triazole-copper triflate coordination compound to fluorobenzoic boric acid and preparation method thereof |
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| CN201410769197.5A CN104557986B (en) | 2014-12-15 | 2014-12-15 | Have and be catalyzed triazole-copper triflate coordination compound to fluorobenzoic boric acid and preparation method thereof |
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