CN104530092B - Oxygen ether bis-triazole copper complex for catalyzing 4-pyridine phenylboronic acid and preparation method thereof - Google Patents
Oxygen ether bis-triazole copper complex for catalyzing 4-pyridine phenylboronic acid and preparation method thereof Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 10
- 229910052760 oxygen Inorganic materials 0.000 title claims description 10
- 239000001301 oxygen Substances 0.000 title claims description 10
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 title abstract description 7
- NAVCONYGKYKXOC-UHFFFAOYSA-N [Cu].N1=NC(N=C1)=C1N=NC=N1 Chemical compound [Cu].N1=NC(N=C1)=C1N=NC=N1 NAVCONYGKYKXOC-UHFFFAOYSA-N 0.000 title 1
- 238000005859 coupling reaction Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- -1 triazole copper complex Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 235000010338 boric acid Nutrition 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 239000000047 product Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 150000004699 copper complex Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 150000003852 triazoles Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical class [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 229960004643 cupric oxide Drugs 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
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 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
- 239000012046 mixed solvent Substances 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 230000035484 reaction time Effects 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
- YAWIAFUBXXPJMQ-UHFFFAOYSA-N 1-bromo-4-(4-bromophenoxy)benzene Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1 YAWIAFUBXXPJMQ-UHFFFAOYSA-N 0.000 description 1
- BIRLDGKMJJEZRI-UHFFFAOYSA-N 1-bromo-4-[1,2,2-tris(4-bromophenyl)ethenyl]benzene Chemical compound C1=CC(Br)=CC=C1C(C=1C=CC(Br)=CC=1)=C(C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 BIRLDGKMJJEZRI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- YAVVGPBYBUYPSR-UHFFFAOYSA-N benzene;oxygen Chemical compound [O].C1=CC=CC=C1 YAVVGPBYBUYPSR-UHFFFAOYSA-N 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 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
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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
- B01J31/1815—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
- 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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- 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
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- 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
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
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Abstract
The invention discloses a preparation method of [Cu(L)2(NO3)2] (1) (L=1-(4-(4-(1H-1,2,4-triazole-1-yl) phenoxyl) phenyl)-1H-1,2,4-triazole), and the [Cu(L)2(NO3)2] (1) (L=1-(4-(4-(1H-1,2,4-triazole-1-yl) phenoxyl) phenyl)-1H-1,2,4-triazole) has a potential application value of catalyzing a coupling reaction of 4-pyridine phenylboronic acid. A normal temperature evaporation method is adopted, namely, the complex is prepared from Cu(NO3)2 and L under a normal temperature stirring volatilization condition. The invention further discloses an application of the [Cu(L)2(NO3)2] (1) (L=1-(4-(4-(1H-1,2,4-triazole-1-yl) phenoxyl) phenyl)-1H-1,2,4-triazole) serving as a coupling reaction catalyst of the 4-pyridine phenylboronic acid.
Description
The present invention obtains state natural sciences fund general project (21471113), Tianjin Municipal Education Commission funded projects
(20140506), Tianjin Normal University's Middl-age and youth faculty Academic innovations propulsion 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, it is related to copper complex [cu (l)2(no3)2] (1) (l = 1-(4-
(4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole) preparation method and as 4- pyridine
The application of the catalyst aspect of phenyl boric acid coupling reaction.
Background technology
One active field is always with the research that transition metal complex catalysis carries out high selectivity.With common
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 of metal complex and develop the organic synthesis of high selectivity, high conversion, be very interesting
Problem.In organic synthesis, typically conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex show many
Sample catalysis.Palladium catalysed cross coupling reaction species is a lot, and these reactions are in synthesis of natural product, polymer, functional material, liquid
All have been widely used in crystalline substance, drug molecule and bioactive compound.But palladium catalyst is relatively costly, if can be with cheap
Copper complex replaces expensive palladium catalyst, realizes the process of reaction, not only can be cost-effective, and is expected to industrial metaplasia
Produce.
1,2,4- triazole and its derivative have the coordination feature of pyrazoles and imidazoles concurrently, are that the stronger bridging of coordination ability is joined
Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound at present.These parts can be former with the nitrogen on 1,2
Son and metallic ion coordination form n1, n2- bridging pattern, and for 4 unsubstituted 1,2,4- triazole derivatives can pass through 2,4
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 dimensions
Metal complex is to complete the vital step of device.
The present invention is from cu (no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-
1,2,4- triazole (l) prepares copper complex [cu (l) under normal temperature condition2(no3)2] (1).Catalysis experiments prove, this is joined
Compound can be applied as the catalyst of 4- pyridine phenyl boric acid coupling reaction.
Content of the invention
Further object is that providing a kind of isophthalic double triazole copper complex [cu (l)2(no3)2] (1) monocrystalline
And preparation method thereof.
For this current inventor provides following technical scheme:
The double triazole copper complex [cu (l) of oxygen ether2(no3)2] (1) (l=1- (4- (4- (1h-1,2,4- triazole -1-
Base) phenoxy group) phenyl) -1h-1,2,4- triazole) structural motif as shown in Figure 1.
The present invention further discloses the double triazole copper complex [cu (l) of oxygen ether2(no3)2] (1) (l = 1-(4-(4-
(1h-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1h-1,2,4- triazoles) monocrystalline it is characterised in that this monocrystalline knot
Structure adopt apex ii ccd single crystal diffractometer, using through graphite monochromatised mok alpha ray (λ=0.71073) be incidence
Radiation, withω-2θScan mode collects point diffraction, obtains cell parameter through least square refinement, from difference Fourier
Electron-density map solves single crystal data using software:
The crystallographic data of table 1. complex 1
The double triazole copper complex [cu (l) of oxygen ether of the present invention2(no3)2] (1) (l = 1-(4-(4-(1h-1,2,4-
Triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazoles) monocrystalline preparation method, its feature is using " normal temperature at it
Volatility process ", i.e. cu (no3)2Get off to obtain to be suitable for the yellow rhabdolith of x- ray single crystal diffraction with l stirring at normal temperature volatilization condition.
Wherein ch3Oh and h2The volume ratio of o is 4:6, cu (no3)2Mol ratio with l is 1:1；
The more detailed preparation method of the present invention is as follows:
A kind of double triazole copper complex [cu (l) of oxygen ether2(no3)2] (1) (l=1- (4- (4- (1h-1,2,4- tri- nitrogen
Azoles -1- base) phenoxy group) phenyl) -1h-1,2,4- triazoles) monocrystalline preparation method, its feature it using " normal temperature volatilize
Method ", i.e. cu (no3)2Get off to obtain to be suitable for the yellow rhabdolith of x- ray single crystal diffraction with l stirring at normal temperature volatilization condition.Wherein
ch3Oh and h2The volume ratio of o is 4:6, cu (no3)2Mol ratio with l is 1:1；
Solvent of the present invention is mixed solvent, ch3Oh and h2o.
Wherein cu (no3)2Mol ratio with l is 1:1.
The present invention further discloses a kind of double triazole copper complex of oxygen ether has catalysis 4- pyridine phenyl boric acid coupling reaction
Effect.
A kind of double triazole copper complex [cu (l) of oxygen ether disclosed by the invention2(no3)2] (1) (l = 1-(4-(4-(1h-
1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole) monocrystalline had the advantage that to be with feature:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) [the cu (l) prepared by the present invention2(no3)2] (1) (l=1- (4- (4- (1h-1,2,4- triazole -1-
Base) phenoxy group) phenyl) -1h-1,2,4- triazoles) low production cost, method simplicity, it is suitable for large-scale production.
Brief description
The crystal structure primitive figure of Fig. 1: complex 1；
The one-dimensional catenary structure figure of Fig. 2: complex 1.
The nuclear-magnetism figure of Fig. 3: 4,4'- bipyridyl.
Specific embodiment
With reference to 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 be bought from chemical reagents corporation both domestic and external, does not have
Use through continuation purification but directly.Wherein cu (no3)2, ch3Oh is by commercially available.
Embodiment 1
The preparation of 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole (l)
In dmf polar solvent, by 1,1,2,2- tetra- (4- bromophenyl) ethene, triazole, potassium carbonate and cupric oxide are in heating
Under the conditions of prepare this organic compound；Wherein 4,4 '-dibromodiphenyl ether: triazole: potassium carbonate: the mol ratio of cupric oxide is 2:10:
30:1；
150 DEG C of reaction temperature, 18 hours reaction time.
Embodiment 2
cu(no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole
L the mol ratio of () is 1:1；
L (0.0304 g, 0.1 mmol) and cu (no3)2(0.0242 g, 0.1 mmol) is in h2O (6 ml) and
ch3Filter after stirring at normal temperature half an hour in the mixed solvent of oh (4 ml), filtrate normal temperature volatilizees what x- ray single crystal diffraction was analyzed
Yellow rhabdolith.Yield: 45% (being calculated based on l).Elementary analysis (c32h24cun14o8) theoretical value (%): c, 48.27；H,
3.04；N, 24.63.Measured value: c, 48.25；H, 3.16；N, 24.66.
Embodiment 3
Crystal structure determination adopts apex ii ccd single crystal diffractometer, using through graphite monochromatised mok alpha ray (λ
=0.71073) it is incident radiation, withω-2θScan mode collects point diffraction, obtains structure cell through least square refinement
Parameter, solves crystal structure from difference Fourier electron-density map using software, and through Lorentz lorentz and polarity effect correction.All
H atom synthesized by difference Fourier and through preferable position calculation determine.Detailed axonometry data is shown in Table 1.Structural motif
See Fig. 1, one-dimensional catenary structure is shown in Fig. 2.
The crystallographic data of table 1. complex 1
Embodiment 4
cu(no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole
L () mol ratio is 1:1；
We also attempted other ratios, such as cu (no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) benzene oxygen
Base) phenyl) -1h-1, the mol ratio of 2,4- triazoles (l) is 2:1, then the length of no matter the hydro-thermal reaction time, all cannot get crystalline substance
State compound.Therefore cu (no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- three
The mol ratio of nitrogen azoles (l) is optimum response proportioning for 1:1.
Embodiment 5
One active field is always with the research that transition metal complex catalysis carries out high selectivity.With common
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 of metal complex and develop the organic synthesis of high selectivity, high conversion, be very interesting
Problem.In organic synthesis, typically conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex show many
Sample catalysis.Palladium catalysed cross coupling reaction species is a lot, and these reactions are in synthesis of natural product, polymer, functional material, liquid
All have been widely used in crystalline substance, drug molecule and bioactive compound.But palladium catalyst is relatively costly, if can be with cheap
Copper complex replaces expensive palladium catalyst, realizes the process of reaction, not only can be cost-effective, and is expected to industrial metaplasia
Produce.
1,2,4- triazole and its derivative have the coordination feature of pyrazoles and imidazoles concurrently, are that the stronger bridging of coordination ability is joined
Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound at present.These parts can be former with the nitrogen on 1,2
Son and metallic ion coordination form n1, n2- bridging pattern, and for 4 unsubstituted 1,2,4- triazole derivatives can pass through 2,4
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 dimensions
Metal complex is to complete the vital step of device.
The present invention is from cu (no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-
1,2,4- triazole (l) prepares copper complex [cu (l) in normal temperature volatilization2(no3)2] (1).Catalysis experiments prove,
This complex can be applied as the catalyst of 4- pyridine phenyl boric acid coupling reaction
1.1 g 4- pyridine phenyl boric acids, 0.2 g cs is weighed in 25 ml beakers2co3, 3 ml dmf and 0.1 g catalyst
(complex 1), stirs 1 hour under room temperature, and tlc monitoring (pe:ea=1:1) reaction is complete, 10 ml ch2cl2After extracted products
Distill water washing, organic phase sewage mgso with 20 ml again4It is dried, filters, precipitation, the crude product obtaining is eluted with petroleum ether
Cross post, obtain 4,4'- bipyridyl.
Claims (2)
1. application in terms of preparation is as the coupling reaction catalyst of 4- pyridine phenyl boric acid for the double triazole copper complex monocrystalline of oxygen ether,
It is characterized in that this mono-crystalline structures adopts apex ii ccd single crystal diffractometer, using through graphite monochromatised mok alpha ray, λ
=0.71073 is incident radiation, withω-2θScan mode collects point diffraction, obtains structure cell through least square refinement
Parameter, solves single crystal data from difference Fourier electron-density map using software:
The molecular formula of the double triazole copper complex monocrystalline of described oxygen ether: [cu (l)2(no3)2], wherein l=1- (4- (4- (1h-1,
2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole.
2. application according to claim 1, the method for wherein 4- pyridine phenyl boric acid coupling reaction is as follows:
1.1 g 4- pyridine phenyl boric acids, 0.2 g cs is weighed in 25 ml beakers2co3, the catalyst of 3 ml dmf and 0.1 g joins
Compound monocrystalline, stirs 1 hour under room temperature, and tlc monitors, 10 ml ch2cl2Distill water washing with 20 ml again after extracted products, have
The anhydrous mgso of machine phase4It is dried, filter, precipitation, the crude product obtaining strips post with petroleum ether, obtains 4,4'- bipyridyl.
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