CN104402913A - Anthracene-ring bis (triazol 1 yl) copper perchlorate complex with catalyst phenylboronic acid and preparation method thereof - Google Patents
Anthracene-ring bis (triazol 1 yl) copper perchlorate complex with catalyst phenylboronic acid and preparation method thereof Download PDFInfo
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- CN104402913A CN104402913A CN201410767590.0A CN201410767590A CN104402913A CN 104402913 A CN104402913 A CN 104402913A CN 201410767590 A CN201410767590 A CN 201410767590A CN 104402913 A CN104402913 A CN 104402913A
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- Prior art keywords
- triazole
- tatrz
- base
- anthracene
- clo
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Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 title abstract 6
- 239000003054 catalyst Substances 0.000 title description 5
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 title 1
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000005859 coupling reaction Methods 0.000 claims abstract 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract 2
- 239000010949 copper Substances 0.000 claims description 30
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 26
- 150000003852 triazoles Chemical class 0.000 claims description 16
- 150000004699 copper complex Chemical class 0.000 claims description 14
- 150000001454 anthracenes Chemical class 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000005260 alpha ray Effects 0.000 claims description 3
- 238000002447 crystallographic data Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 abstract 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 abstract 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 5
- 229960004643 cupric oxide Drugs 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000004044 response Effects 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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000008569 process Effects 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
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- -1 triazole copper complex Chemical class 0.000 description 2
- 238000004458 analytical method Methods 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
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of {[Cu(tatrz)2(H2O)2](ClO4)2*4CH3OH}( 1 )(tatrz=1-[9-(1H-1,2,4-triazole-1-yl)anthracene-10-yl]-1H-1,2,4-triazole) and a potential application value in catalyzing a phenylboronic acid coupled reaction. The complex is prepared by using a room temperature volatilization method, namly stirring and volatilizing Cu(ClO4)2 and tatrz at room temperature. The invention further discloses an application of the {[Cu(tatrz)2(H2O)2](ClO4)2*4CH3OH}( 1 )(tatrz=1-[9-(1H-1,2,4-triazole-1-yl)anthracene-10-yl]-1H-1,2,4-triazole) in a factor of a coupled reaction catalyst of phenylboronic 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 to subsidize (TD12-5038).
Technical field
The invention belongs to Inorganic synthese technical field, relate to copper complex { [Cu (tatrz)
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1) application of the preparation method of (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) and the catalyzer aspect as phenylo boric acid linked reaction.
Background technology
The research carrying out high selectivity with transition metal complex catalysis is an active field always.Be difficult to the reaction realized with common synthesizing mean, busy use transition metal complex can a step complete in a mild condition.Therefore, adopting metal complex to make catalyzer to develop the organic synthesis of highly selective, high conversion, is very interesting problem.In organic synthesis, general conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex demonstrates diversity catalysis.Palladium catalysed cross coupling reaction kind is a lot, and these reactions all have been widely used in synthesis of natural product, polymkeric substance, functional materials, liquid crystal, drug molecule and bioactive compounds.But palladium catalyst is relatively costly, if can replace expensive palladium catalyst with cheap copper complex, the process of realization response, not only can be cost-saving, and be expected to suitability for industrialized production.
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridgingligands that coordination ability is stronger, have synthesized at present and have characterized a large amount of monokaryons, multinuclear and multidimensional compound.These parts can with 1, nitrogen-atoms on 2 and metallic ion coordination form N1, N2-bridging pattern, for 4 unsubstituted 1,2,4-triazole derivative is by 2, nitrogen-atoms on 4 forms N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, and N3-bridging mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
The present invention selects Cu (ClO
4)
2under normal temperature condition, copper complex { [Cu (tatrz) is prepared with 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz)
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1).Catalysis experiments proves, the catalyzer that this title complex can be used as phenylo boric acid linked reaction is applied.
Summary of the invention
Another object of the present invention is to provide a kind of anthracene nucleus two triazole copper complex { [Cu (tatrz)
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) monocrystalline and preparation method thereof.
Current inventor provides following technical scheme for this reason:
Two triazole the copper complex { [Cu (tatrz) of anthracene nucleus
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) structural motif as shown in Figure 1.
The present invention further discloses two triazole the copper complex { [Cu (tatrz) of anthracene nucleus
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-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 the copper complex { [Cu (tatrz) of anthracene nucleus of the present invention
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1) preparation method of (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) monocrystalline, its feature is adopt " normal temperature volatilization method ", i.e. Cu (ClO at it
4)
2get off to obtain the yellow rhabdolith of applicable X-ray single crystal diffraction with tatrz stirring at normal temperature volatilization condition.Wherein CH
3cN and H
2the volume ratio of O is 4:6, Cu (ClO
4)
2be 1:1 with the mol ratio of tatrz;
The more detailed preparation method of the present invention is as follows:
Two triazole the copper complex { [Cu (tatrz) of a kind of anthracene nucleus
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1) preparation method of (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) monocrystalline, its feature adopts " normal temperature volatilization method ", i.e. Cu (ClO at it
4)
2get off to obtain the yellow rhabdolith of applicable X-ray single crystal diffraction with tatrz stirring at normal temperature volatilization condition.Wherein CH
3cN and H
2the volume ratio of O is 4:6, Cu (ClO
4)
2be 1:1 with the mol ratio of tatrz;
Solvent of the present invention is mixed solvent, CH
3cN and H
2o.
Wherein Cu (ClO
4)
2be 1:1 with the mol ratio of tatrz.
The present invention further discloses the effect that the two triazole copper complex of a kind of anthracene nucleus has catalysis phenylo boric acid linked reaction.
Two triazole the copper complex { [Cu (tatrz) of a kind of anthracene nucleus disclosed by the invention
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1) advantage and disadvantage that has of (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-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 (tatrz) prepared by the present invention
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) production cost is low, method is easy, is applicable to scale operation.
Accompanying drawing explanation
Fig. 1: title complex
1crystalline structure primitive figure;
Fig. 2: title complex
1tomograph.
Fig. 3: the nuclear-magnetism figure of biphenyl.
Embodiment
Below in conjunction with embodiment, the present invention is described further, and embodiment is only indicative, never means that it limits the scope of the invention by any way.All raw materials are such as: anthracene nucleus etc. are all buy from chemical reagents corporation both domestic and external, through continuing to purify but directly use.Wherein Cu (ClO
4)
2, CH
3oH is by commercially available.
Embodiment 1
The preparation of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz) part
1-of the present invention [9-(1H-1,2,4-triazole-1-base) anthracene-10-base] preparation method of-1H-1,2,4-triazole, its feature is in employing " one kettle way ", in polar solvent, by 9,10-dibromoanthracene, triazole, this organic compound prepared in a heated condition by salt of wormwood and cupric oxide; Wherein 9,10-dibromoanthracenes: triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1;
The present invention is 9,10-dibromoanthracenes (I) preferably: triazole (II): salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1; Temperature of reaction 80-200 DEG C, reaction times 12-120 hour.
The more detailed preparation method of the present invention is as follows:
A kind of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base] preparation method of-1H-1,2,4-triazole is characterized in that, in polar solvent, adopt " one kettle way ", by 9,10-dibromoanthracene, triazole, this organic compound prepared in a heated condition by salt of wormwood and cupric oxide;
Polar solvent of the present invention is DMF.
Wherein 9,10-dibromoanthracenes: triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10-15:30:1;
Embodiment 2
Cu (ClO
4)
2be 1:1 with the mol ratio of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz);
Tatrz (0.0312 g, 0.1 mmol) and Cu (ClO
4)
2(0.0370 g, 0.1 mmol) is at H
2o (6 mL) and CH
3in the mixed solvent of OH (4 mL), stirring at normal temperature was filtered after half an hour, the yellow rhabdolith that filtrate normal temperature volatilization X-ray single crystal diffraction is analyzed.Productive rate: 35% (calculating based on tatrz).Ultimate analysis (C
40h
44cl
2cuN
12o
14) theoretical value (%): C, 45.70; H, 4.22; N, 15.99.Measured value: C, 45.75; H, 4.12; N, 15.89.
Embodiment 2
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 inclusion anthracene nucleus molecule is shown in Fig. 2 as the two-dimensional layered structure of organic formwork.
Table 1. title complex
1crystallographic data
Embodiment 3
Cu (ClO
4)
2be 1:1 with the mol ratio of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz);
We also attempted other ratios, such as Cu (ClO
4)
2be 2:1 with the mol ratio of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz), then the length of no matter hydro-thermal reaction time, all can not get crystalline compound.Therefore Cu (ClO
4)
2be 1:1 with the mol ratio of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz) be optimum response proportioning.
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 (ClO
4)
2under normal temperature volatilization condition, copper complex { [Cu (tatrz) is prepared with 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (tatrz)
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1).Catalysis experiments proves, the catalyzer that this title complex can be used as phenylo boric acid linked reaction is applied
1 g phenylo boric acid is taken, 0.2 g Cs in 25 mL beakers
2cO
3, 3 mL DMF and 0.1 g catalyzer (title complex
1), stirred at ambient temperature 1 hour, TLC monitoring (PE:EA=1:1) reacts completely, 10 mLCH
2cl
220 mL distilled water washs are used again, organic phase sewage MgSO after extracted products
4drying, filter, precipitation, the thick product obtained strips post with sherwood oil, obtains biphenyl.
Claims (4)
1. two triazole the copper complex { [Cu (tatrz) of anthracene nucleus
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) structural motif as shown in Figure 1.
2. the monocrystalline of copper complex described in claim 1, is characterized in that this single crystal structure adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with
ω-2
θscan mode collects point diffraction, obtains unit cell parameters, utilize software to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex
1crystallographic data
。
3. the { [Cu (tatrz) of copper complex described in claim 1
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1) preparation method of (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole), it is characterized in that it adopts " normal temperature volatilization method ", i.e. Cu (ClO
4)
2get off to prepare this title complex with tatrz stirring at normal temperature volatilization condition;
Described solvent is mixed solvent is CH
3oH and H
2o; Wherein Cu (ClO
4)
2be 1:1 with the mol ratio of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (L).
4. the { [Cu (tatrz) of copper complex described in claim 1
2(H
2o)
2] (ClO
4)
24CH
3oH} (
1) (tatrz=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole) can be used as the application of the coupling reaction catalyst aspect of phenylo boric acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418647A (en) * | 2016-01-05 | 2016-03-23 | 天津师范大学 | Anthracene nucleus di-triazole three-dimensional copper nitrate complex single crystal and application |
| CN106397785A (en) * | 2016-09-12 | 2017-02-15 | 广西师范大学 | 3-carboxyl-1, 2, 4-triazole copper coordination polymer and in-situ synthesis method thereof |
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Non-Patent Citations (3)
| Title |
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| JU-YAN LIU ET AL.: "Anion-Exchange and Anthracene-Encapsulation within Copper(II) and Manganese(II)-Triazole Metal-Organic Confined Space in a Single Crystal-to-Single Crystal Transformation Fashion", 《INORG. CHEM.》, vol. 53, no. 12, 27 May 2014 (2014-05-27), pages 5972 - 5985 * |
| KASI PITCHUMANI ET AL.: "Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal–organic frameworks", 《GREEN CHEMISTRY》, vol. 16, 24 February 2014 (2014-02-24), pages 2865 - 2875 * |
| N KIRAI ET AL.: "Homocoupling of Arylboronic Acids Catalyzed by 1,10-Phenanthroline-Ligated Copper Complexes in Air", 《EUR. J. ORG. CHEM.》, vol. 12, 31 December 2009 (2009-12-31), pages 1864 - 1867 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418647A (en) * | 2016-01-05 | 2016-03-23 | 天津师范大学 | Anthracene nucleus di-triazole three-dimensional copper nitrate complex single crystal and application |
| CN106397785A (en) * | 2016-09-12 | 2017-02-15 | 广西师范大学 | 3-carboxyl-1, 2, 4-triazole copper coordination polymer and in-situ synthesis method thereof |
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