CN104530093B - Triazole-copper tetrafluoroborate complex for catalyzing 4-methoxyphenylboronic acid and preparation method thereof - Google Patents
Triazole-copper tetrafluoroborate complex for catalyzing 4-methoxyphenylboronic acid and preparation method thereof Download PDFInfo
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- CN104530093B CN104530093B CN201410767940.3A CN201410767940A CN104530093B CN 104530093 B CN104530093 B CN 104530093B CN 201410767940 A CN201410767940 A CN 201410767940A CN 104530093 B CN104530093 B CN 104530093B
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- -1 Triazole-copper tetrafluoroborate Chemical compound 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 10
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 title abstract 4
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 claims description 9
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 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 abstract description 12
- 239000010949 copper Substances 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 229910017981 Cu(BF4)2 Inorganic materials 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 7
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000005260 alpha ray Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 230000015689 metaplastic ossification Effects 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 230000005855 radiation 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
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 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
- 238000002050 diffraction method Methods 0.000 description 1
- 239000012153 distilled water Substances 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
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
-
- 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)
- Catalysts (AREA)
Abstract
The invention relates to a triazole-copper tetrafluoroborate complex for catalyzing 4-methoxyphenylboronic acid and a preparation method thereof, and discloses a preparation method of {[Cu(L)](BF4)2.0.5H2O} (1) (L = 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole), and the {[Cu(L)](BF4)2.0.5H2O} (1) (L = 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) has a potential application value of a coupling reaction catalyst of 4-methoxyphenylboronic acid. A hydrothermal method is adopted, namely, the complex is prepared from Cu(BF4)2 and L under a hydrothermal condition of 100 DEG C. The invention further discloses an application of the {[Cu(L)](BF4)2.0.5H2O} (1) (L = 4-(3-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole) serving as the coupling reaction catalyst of the 4-methoxyphenylboronic 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)] (clo4)·0.25h2o} (1) (l
=4- (3- (4h-1,2,4- triazole-4-yl) phenyl) -4h-1,2,4- triazole) preparation method and as even to methylphenylboronic acid
The application of the catalyst aspect of connection 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 synthesiss, typically conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex show many
Sample catalysiss.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 derivant 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 (bf4)2With 4- (3- (4h-1,2,4- triazole-4-yl) phenyl) -4h-1,2,4- triazole
L () is 100oC hydrothermal condition gets off to prepare copper complex { [cu (l)] (bf4)2·0.5h2o} (1).Catalysis experiments prove, should
Coordination compound can be applied as to the catalyst of methylphenylboronic acid coupling reaction.
Content of the invention
Further object is that providing a kind of isophthalic double triazole copper complex { [cu (l)] (bf4)2·
0.5h2O } (1) monocrystalline and preparation method thereof.
For this current inventor provides following technical scheme:
Double triazole copper complex { [cu (l)] (bf of isophthalic4)2·0.5h2O } (1) (l=4- (3- (4h-1,2,4- tri-
Azoles -4- base) phenyl) -4h-1,2,4- triazole) and structural motif as shown in Figure 1.
The present invention further discloses double triazole copper complex { [cu (l)] (bf of isophthalic4)2·0.5h2o} (1) (l =
4- (3- (4h-1,2,4- triazole-4-yls) phenyl) -4h-1,2,4- triazoles) monocrystalline is it is characterised in that this mono-crystalline structures adopts
Apex ii ccd single crystal diffractometer, using through graphite monochromatised mok alpha ray (λ=0.71073) be incident radiation,
Withω-2θScan mode collects point diffraction, obtains cell parameter through least square refinement, close from difference Fourier electronics
Degree is desired to make money or profit and is solved single crystal data with software:
The crystallographic data of table 1. coordination compound 1
Double triazole copper complex { [cu (l)] (bf of isophthalic of the present invention4)2·0.5h2o} (1) (l = 4-(3-(4h-
1,2,4- triazole-4-yl) phenyl) -4h-1,2,4- triazoles) monocrystalline preparation method, its feature adopt " hydro-thermal method ",
ch3Cn and h2In o, by cu (bf4)2With l ligand 1 00oReact under c hydrothermal condition, obtain being suitable for the yellow of x- ray single crystal diffraction
Rhabdolith.Wherein ch3Cn and h2The volume ratio of o is 4:6, cu (bf4)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)] (bf of isophthalic4)2·0.5h2o} (1) (l = 4-(3-(4h-1,2,4-
Triazole-4-yl) phenyl) -4h-1,2,4- triazoles) monocrystalline preparation method, its feature adopt " hydro-thermal method ", in ch3Cn and h2o
In, by cu (bf4)2With l ligand 1 00oReact under c hydrothermal condition, obtain being suitable for the yellow rhabdolith of x- ray single crystal diffraction.
Wherein ch3Cn and h2The volume ratio of o is 4:6, cu (bf4)2Mol ratio with l is 1:1；
Solvent of the present invention is mixed solvent, ch3Cn and h2o.
Wherein cu (bf4)2Mol ratio with l is 1:1.
The present invention further discloses a kind of double triazole copper complex of isophthalic has catalysis to methylphenylboronic acid coupling reaction
Effect.
A kind of double triazole copper complex { [cu (l)] (bf of isophthalic disclosed by the invention4)2·0.5h2o} (1) (l = 4-
(3- (4h-1,2,4- triazole-4-yl) phenyl) -4h-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) { [cu (l)] (bf prepared by the present invention4)2·0.5h2O } (1) (l=4- (3- (4h-1,2,4- tri-
Azoles -4- base) phenyl) -4h-1,2,4- triazoles) low production cost, method simplicity, suitable large-scale production.
Brief description
The crystal structure primitive figure of Fig. 1: coordination compound 1；
The tomograph of Fig. 2: coordination compound 1.
The nuclear-magnetism figure of Fig. 3: 4,4'- dimethyl diphenyl.
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 (bf4)2, ch3Cn is by commercially available.
Embodiment 1
The preparation of 4- (3- (4h-1,2,4- triazole-4-yl) phenyl) -4h-1,2,4- triazole (l) part
It is separately added into m-diaminobenzene. (1 in the 50 ml three neck round bottom flasks equipped with magneton, reflux condenser and thermometer
Mmol), double formylhydrazines (2 mmol), start stirring at 160 DEG C, react 12 hours.After reaction terminates, reactant liquor is down to room
Temperature, separates out a large amount of precipitation, by precipitation water and ethyl alcohol recrystallization, yield 86%.Elementary analysiss c10h8n6Theoretical value: c, 56.60;
h, 3.80; n, 39.60.Experiment value: c, 56.56; h, 3.75; n, 39.56.M-diaminobenzene., double formylhydrazines mole
Than for 1:2.
Embodiment 2
cu(bf4)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 (bf4)2(0.0691 g, 0.2 mmol), h2O (6 ml), ch3cn
(4 ml), hydro-thermal 100oC was slowly dropped to room temperature after tri- days.There is the yellow of suitable x- ray single crystal diffraction analysis bar-shaped after driving kettle
Crystal.Yield: 35% (being calculated based on l).Elementary analysiss (c10h9bcuf4n6o0.5) theoretical value (%): c, 32.32；H, 2.44；N,
22.62.Measured value: c, 32.35；H, 2.46；N, 22.69.
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, the three dimensional structure of coordination compound is shown in Fig. 2.
The crystallographic data of table 1. coordination compound 1
Embodiment 4
cu(bf4)2With 4- (3- (4h-1,2,4- triazole-4-yl) phenyl) -4h-1,2,4- triazole) mol ratio of (l) is 1:
1；
We also attempted other ratios, such as cu (bf4)2With-(3- (4h-1,2,4- triazole-4-yl) phenyl) -4h-1,
2,4- triazoles) mol ratio be 2:1, then the length of no matter the hydro-thermal reaction time, all cannot get crystalline compound.Therefore cu
(bf4)2With-(3- (4h-1,2,4- triazole-4-yl) phenyl) -4h-1,2,4- triazole) mol ratio be that optimum response is joined for 1:1
Than.
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 synthesiss, typically conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex show many
Sample catalysiss.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 derivant 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 (bf4)2With 4- (3- (4h-1,2,4- triazole-4-yl) phenyl) -4h-1,2,4- triazole
L () is 100oC hydrothermal condition gets off to prepare copper complex { [cu (l)] (bf4)2·0.5h2o} (1).Catalysis experiments prove, should
Coordination compound can be applied as to the catalyst of methylphenylboronic acid coupling reaction.
Weigh 1.1 g to methylphenylboronic acid in 25 ml beakers, 0.2 g cs2co3, 3 ml dmf and 0.1 g catalyst
(coordination compound 1), stirs 1 hour under room temperature, and tlc monitoring (pe:ea=1:1) reaction is complete, 10 ml ch2cl2After extracted products
Again with 20 ml distilled water washs, organic faciess sewage mgso4It is dried, filter, precipitation, the crude product obtaining is with petroleum ether eluting
Cross post, obtain 4,4'- dimethyl diphenyl.
Claims (1)
1. application in terms of as the coupling reaction catalyst to methylphenylboronic acid for the double triazole copper complex of isophthalic, described isophthalic
The molecular formula of double triazole copper complexes is: [cu (l)] (bf4)2·0.5h2O, part l is: 4- (3- (4h-1,2,4- triazole -4-
Base) phenyl) -4h-1,2,4- triazoles, and the described complex-catalyzed method to methylphenylboronic acid coupling reaction is as follows:
To methylphenylboronic acid 4,4'- dimethyl diphenyl
Weigh 1.1 g to methylphenylboronic acid in 25 ml beakers, 0.2 g cs2co3, 3 ml dmf and 0.1 g catalyst complex
Thing monocrystalline, stirs 1 hour under room temperature, and tlc monitoring reaction is complete, 10 ml ch2cl2Again with 20 ml distillation washings after extracted products
Wash, the anhydrous mgso of organic faciess4It is dried, filter, precipitation, the crude product obtaining strips post with petroleum ether, obtains 4,4'- diformazan
Base biphenyl.
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