CN104497020A - Triazole and copper perchlorate complex with 4-pyridinylphenylboronic acid catalyzing effect and preparation method of triazole and copper perchlorate complex - Google Patents
Triazole and copper perchlorate complex with 4-pyridinylphenylboronic acid catalyzing effect and preparation method of triazole and copper perchlorate complex Download PDFInfo
- Publication number
- CN104497020A CN104497020A CN201410768491.4A CN201410768491A CN104497020A CN 104497020 A CN104497020 A CN 104497020A CN 201410768491 A CN201410768491 A CN 201410768491A CN 104497020 A CN104497020 A CN 104497020A
- Authority
- CN
- China
- Prior art keywords
- triazole
- clo
- phenyl
- complex
- copper complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- BANFGGCAQWUIAJ-UHFFFAOYSA-N (4-pyridin-2-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=CC=N1 BANFGGCAQWUIAJ-UHFFFAOYSA-N 0.000 title abstract 2
- 150000003852 triazoles Chemical class 0.000 title description 4
- 230000000694 effects Effects 0.000 title description 2
- 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 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims description 29
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 10
- 150000004699 copper complex Chemical class 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 7
- 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
- -1 triazole copper complex Chemical class 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
- 230000005855 radiation Effects 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract 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
- 229910052763 palladium Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 7
- 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
- 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 4
- 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
- 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
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000975 bioactive effect Effects 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
- 238000002474 experimental method Methods 0.000 description 2
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 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
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 239000002994 raw material Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CDLQWUMKNSKGET-UHFFFAOYSA-N C[I](NN=C1)N1c1cccc(-[n]2cnnc2)c1 Chemical compound C[I](NN=C1)N1c1cccc(-[n]2cnnc2)c1 CDLQWUMKNSKGET-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 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
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000010865 sewage 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
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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)
- Plural Heterocyclic Compounds (AREA)
- Catalysts (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a preparation method of {[Cu(L)] (ClO4).0.25H2O} (1) (L=4-(3-(4H-1, 2, 4-triazole-4-yl)phenyl)-4H-1, 2, 4-triazole). The complex is prepared by using a hydrothermal method comprising the step of reacting Cu(ClO4)2 and L under a 100-DEG C hydrothermal condition. The invention further discloses application of {[Cu(L)] (ClO4).0.25H2O} (1) (L=4-(3-(4H-1, 2, 4-triazole-4-yl)phenyl)-4H-1, 2, 4-triazole) as a catalyst for coupled reaction of 4-pyridinylphenylboronic 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 (L)] (ClO
4) 0.25H
2o} (
1) application of the preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) and the catalyzer aspect as 4-pyridine phenylo boric acid linked reaction.
Background technology
The research carrying out high selectivity with transition metal complex catalysis is an active field always.Be difficult to the reaction realized with common synthesizing mean, busy use transition metal complex can a step complete in a mild condition.Therefore, adopting metal complex to make catalyzer to develop the organic synthesis of highly selective, high conversion, is very interesting problem.In organic synthesis, general conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex demonstrates diversity catalysis.Palladium catalysed cross coupling reaction kind is a lot, and these reactions all have been widely used in synthesis of natural product, polymkeric substance, functional materials, liquid crystal, drug molecule and bioactive compounds.But palladium catalyst is relatively costly, if can replace expensive palladium catalyst with cheap copper complex, the process of realization response, not only can be cost-saving, and be expected to suitability for industrialized production.
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridgingligands that coordination ability is stronger, have synthesized at present and have characterized a large amount of monokaryons, multinuclear and multidimensional compound.These parts can with 1, nitrogen-atoms on 2 and metallic ion coordination form N1, N2-bridging pattern, for 4 unsubstituted 1,2,4-triazole derivative is by 2, nitrogen-atoms on 4 forms N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, and N3-bridging mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
The present invention selects Cu (ClO
4)
2with 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100
oc hydrothermal condition gets off to prepare copper complex { [Cu (L)] (ClO
4) 0.25H
2o} (
1).Catalysis experiments proves, the catalyzer that this title complex can be used as 4-pyridine phenylo boric acid linked reaction is applied.
Summary of the invention
Another object of the present invention is to provide a kind of isophthalic two triazole copper complex { [Cu (L)] (ClO
4) 0.25H
2o} (
1) monocrystalline and preparation method thereof.
Current inventor provides following technical scheme for this reason:
Two triazole copper complex { [Cu (L)] (ClO of isophthalic
4) 0.25H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) structural motif as shown in Figure 1; L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole;
The present invention further discloses two triazole copper complex { [Cu (L)] (ClO of isophthalic
4) 0.25H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline, it is characterized in that this single crystal structure adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with
ω-2
θscan mode collects point diffraction, obtains unit cell parameters, utilize software to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex
1crystallographic data
Two triazole copper complex { [Cu (L)] (ClO of isophthalic of the present invention
4) 0.25H
2o} (
1) preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline, its feature in employing " hydrothermal method ", at CH
3cN and H
2in O, by Cu (ClO
4)
2with L ligand 1 00
oreact under C hydrothermal condition, obtain the yellow rhabdolith of applicable X-ray single crystal diffraction.Wherein CH
3cN and H
2the volume ratio of O is 4:6, Cu (ClO
4)
2be 1:1 with the mol ratio of L;
The more detailed preparation method of the present invention is as follows:
Two triazole copper complex { [Cu (L)] (ClO of a kind of isophthalic
4) 0.25H
2o} (
1) preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline, its feature in employing " hydrothermal method ", at CH
3cN and H
2in O, by Cu (ClO
4)
2with L ligand 1 00
oreact under C hydrothermal condition, obtain the yellow rhabdolith of applicable X-ray single crystal diffraction.Wherein CH
3cN and H
2the volume ratio of O is 4:6, Cu (ClO
4)
2be 1:1 with the mol ratio of L;
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 L.
The present invention further discloses copper complex { [Cu (L)] (ClO
4) 0.25H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) as the application of 4-pyridine phenylo boric acid coupling reaction catalyst aspect.
Two triazole copper complex { [Cu (L)] (ClO of a kind of isophthalic disclosed by the invention
4) 0.25H
2o} (
1) advantage and disadvantage that has of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) monocrystalline is:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) { [Cu (L)] (ClO prepared by the present invention
4) 0.25H
2o}
n(
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) production cost is low, method is easy, is applicable to scale operation.
Accompanying drawing explanation
Fig. 1: title complex
1crystalline structure primitive figure;
Fig. 2: title complex
1tomograph;
The nuclear-magnetism figure of Fig. 3: 4,4'-dipyridyl.
Embodiment
Below in conjunction with embodiment, the present invention is described further, and embodiment is only indicative, never means that it limits the scope of the invention by any way.All raw materials are all buy from chemical reagents corporation both domestic and external, through continuation purify but directly use.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
In 50 mL, tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, add mphenylenediamine (1 mmol) respectively, two formyl hydrazine (2 mmol), starts and is stirred in 160 DEG C, reacts 12 hours.After reaction terminates, reaction solution is down to room temperature, separates out and precipitate in a large number, by precipitation water and ethyl alcohol recrystallization, yield 86%.Ultimate analysis C
10h
8n
6theoretical value: C, 56.60; H, 3.80; N, 39.60.Experimental value: C, 56.56; H, 3.75; N, 39.56.Mphenylenediamine, the mol ratio of two formyl hydrazine is 1:2.
Embodiment 2
Cu (ClO
4)
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 (ClO
4)
2(0.0691 g, 0.2 mmol), H
2o (6 mL), CH
3cN (4 mL), hydro-thermal 100
oc is slowly down to room temperature in tri-days afterwards.The yellow rhabdolith that applicable X-ray single crystal diffraction is analyzed is had after driving still.Productive rate: 35% (calculating based on L).Ultimate analysis (C
10h
8.5clCuN
6o
4.25) 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 (ClO
4)
2be 2:1 with the mol ratio of L, then the length of no matter hydro-thermal reaction time, all can not get crystalline compound.Therefore Cu (ClO
4)
2be 1:1 with the mol ratio of L be optimum response proportioning.
Embodiment 3
Crystal structure determination adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with
ω-2
θscan mode collects point diffraction, obtains unit cell parameters, utilize software to solve crystalline structure from difference Fourier electron density map through least-squares refinement, and through Lorentz lorentz and polarizing effect correction.All H atom are synthesized by difference Fourier and are determined through desirable position calculation.Detailed axonometry data are in table 1.Structural motif is shown in Fig. 1, and the three-dimensional structure of title complex is shown in Fig. 2.
Table 1 title complex
1crystallographic data
Embodiment 4
The research carrying out high selectivity with transition metal complex catalysis is an active field always.Be difficult to the reaction realized with common synthesizing mean, busy use transition metal complex can a step complete in a mild condition.Therefore, adopting metal complex to make catalyzer to develop the organic synthesis of highly selective, high conversion, is very interesting problem.In organic synthesis, general conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex demonstrates diversity catalysis.Palladium catalysed cross coupling reaction kind is a lot, and these reactions all have been widely used in synthesis of natural product, polymkeric substance, functional materials, liquid crystal, drug molecule and bioactive compounds.But palladium catalyst is relatively costly, if can replace expensive palladium catalyst with cheap copper complex, the process of realization response, not only can be cost-saving, and be expected to suitability for industrialized production.
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridgingligands that coordination ability is stronger, have synthesized at present and have characterized a large amount of monokaryons, multinuclear and multidimensional compound.These parts can with 1, nitrogen-atoms on 2 and metallic ion coordination form N1, N2-bridging pattern, for 4 unsubstituted 1,2,4-triazole derivative is by 2, nitrogen-atoms on 4 forms N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, and N3-bridging mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
The present invention selects Cu (ClO
4)
2with 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole (L) 100
oc hydrothermal condition gets off to prepare copper complex { [Cu (L)] (ClO
4) 0.25H
2o} (
1).Catalysis experiments proves, the catalyzer that this title complex can be used as 4-pyridine phenylo boric acid linked reaction is applied.
1 g 4-pyridine 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 mL CH
2cl
220 mL distilled water washs are used again, organic phase sewage MgSO after extracted products
4drying, filter, precipitation, the thick product obtained strips post with sherwood oil, obtains 4,4'-dipyridyl.
Claims (4)
1. two triazole copper complex { [Cu (L)] (ClO of isophthalic
4) 0.25H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) structural motif as shown in Figure 1.
2. the monocrystalline of copper complex described in claim 1, is characterized in that this single crystal structure adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with
ω-2
θscan mode collects point diffraction, obtains unit cell parameters, utilize software to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex
1crystallographic data
。
3. { [Cu (L)] (ClO of copper complex described in claim 1
4) 0.25H
2o}
n(
1) preparation method of (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole), it is characterized in that adopting it to be adopt " hydrothermal method ", i.e. Cu (ClO
4)
2with L 100
oc hydrothermal condition gets off and prepares this title complex;
Described solvent is mixed solvent is CH
3cN and H
2o; Wherein Cu (ClO
4)
2be 1:1 with the mol ratio of L.
4. { [Cu (L)] (ClO of copper complex described in claim 1
4) 0.25H
2o} (
1) (L=4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) catalyzer of can be used as 4-pyridine phenylo boric acid linked reaction applied.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410768491.4A CN104497020B (en) | 2014-12-15 | 2014-12-15 | There is triazole-cupric perchlorate coordination compound of catalysis 4-pyridine phenylboric acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410768491.4A CN104497020B (en) | 2014-12-15 | 2014-12-15 | There is triazole-cupric perchlorate coordination compound of catalysis 4-pyridine phenylboric acid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104497020A true CN104497020A (en) | 2015-04-08 |
| CN104497020B CN104497020B (en) | 2016-08-17 |
Family
ID=52938490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410768491.4A Expired - Fee Related CN104497020B (en) | 2014-12-15 | 2014-12-15 | There is triazole-cupric perchlorate coordination compound of catalysis 4-pyridine phenylboric acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104497020B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2014
- 2014-12-15 CN CN201410768491.4A patent/CN104497020B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| PILLAIYAR PUTHIARAJ, ET AL.: "Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal-organic frameworks", 《GREEN CHEM.》, vol. 16, 24 February 2014 (2014-02-24), pages 2865 - 2875 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104497020B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104497018A (en) | Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex | |
| CN104513261A (en) | Oxylether bistriazole for catalysis of 4-tert-butylphenylboronic acid and preparation method thereof | |
| CN104557980A (en) | Triazole-copper trifluoromethanesulfonate complex capable of catalyzing 4-tert-butylphenylboronic acid and preparation method of triazole-copper trifluoromethanesulfonate complex | |
| CN104402913A (en) | Anthracene-ring bis (triazol 1 yl) copper perchlorate complex with catalyst phenylboronic acid and preparation method thereof | |
| CN104447809A (en) | Anthracene ring bitriazole-cupric tetrafluoroborate complex capable of catalyzing p-fluorophenylboronic acid and preparation method of complex | |
| CN104447816A (en) | Triazole and copper fluoroborate complex with p-fluorophenylboronic acid catalysis effect and preparation method of triazole and copper fluoroborate complex | |
| CN104497023B (en) | There is the two triazole-Tetrafluoroboric acid copper complex of anthracene nucleus and its preparation method of catalysis 4-pyridine phenylo boric acid | |
| CN104530096B (en) | Triazole-Tetrafluoroboric acid copper complex with catalysis 4-pyridine phenylo boric acid and preparation method thereof | |
| CN104497022B (en) | Triazole-cupric perchlorate title complex with catalysis 4-tert-butylbenzeneboronic acid and preparation method thereof | |
| CN104447810B (en) | Triazole-copper triflate title complex with catalysis 3-methoxyphenylboronic acid and preparation method thereof | |
| CN104447807B (en) | Triazole-Tetrafluoroboric acid copper complex with catalysis phenylo boric acid and preparation method thereof | |
| CN104478902B (en) | Triazole-Tetrafluoroboric acid copper complex with catalysis 3-methoxyphenylboronic acid and preparation method thereof | |
| CN104557986A (en) | Triazole-copper trifluoromethane sulfonate complex capable of catalyzing p-fluoro-phenyl boric acid and preparation method of triazole-copper trifluoromethane sulfonate complex | |
| CN104497020A (en) | Triazole and copper perchlorate complex with 4-pyridinylphenylboronic acid catalyzing effect and preparation method of triazole and copper perchlorate complex | |
| CN104530097A (en) | Anthracycline bis-triazole-copper tetrafluoroborate complex for catalyzing phenylboronic acid and preparation method thereof | |
| CN104497024A (en) | Triazole-copper perchlorate complex with 3-methoxyphenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex | |
| CN104447814A (en) | Anthracycline bitriazole and copper fluoroborate complex with 4-methoxyphenylboronic acid catalysis effect and preparation method of anthracycline bitriazole and copper fluoroborate complex | |
| CN104447808A (en) | Triazole-copper perchlorate complex capable of catalyzing phenylboronic acid and preparation method of complex | |
| CN104530094A (en) | Triazole-copperperchlorate hydrate complex for catalyzing 4-methoxyphenylboronic acid and preparation method thereof | |
| CN104447812A (en) | Triazole and copper perchlorate complex with p-tolylboronic acid catalysis effect and preparation method of triazole and copper perchlorate complex | |
| CN104478904A (en) | Anthracene-ring bitriazol-cupric tetrafluoroborate complex capable of catalyzing 4-tert-butyl phenylboronic acid and preparation method thereof | |
| CN104478903A (en) | Anthracene-ring bitriazol-cupric tetrafluoroborate complex capable of catalyzing 3-methoxy phenylboronic acid and preparation method thereof | |
| CN104497025A (en) | Anthracycline bitriazole and copper fluoroborate complex with 4-methylbenzeneboronic acid catalyzing effect and preparation method of anthracycline bitriazole and copper fluoroborate complex | |
| CN104860965A (en) | Triazole-copper(II) trifluoromethanesulfonate complex for catalysis of 4-pyridine phenylboronic acid and preparation method therefor | |
| CN104497021A (en) | Triazole and copper fluoroborate complex with 4-methoxyphenylboronic acid catalyzing effect and preparation method of triazole and copper fluoroborate complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20161215 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |