CN105237580A - Bi-di triazole macrocyclic metal complex and synthesizing method and application thereof - Google Patents

Bi-di triazole macrocyclic metal complex and synthesizing method and application thereof Download PDF

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CN105237580A
CN105237580A CN201510670263.8A CN201510670263A CN105237580A CN 105237580 A CN105237580 A CN 105237580A CN 201510670263 A CN201510670263 A CN 201510670263A CN 105237580 A CN105237580 A CN 105237580A
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title complex
triazole
metal complex
synthetic method
macrocyclic metal
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黄富平
黄德茵
边贺东
李海叶
于青
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Guangxi Normal University
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Abstract

The invention discloses a bi-di triazole macrocyclic metal complex and a synthesizing method and application thereof. The synthesizing method of the bi-di triazole macrocyclic metal complex includes the step of putting 5,5-diamido-1H, 1H-3,3'-bi-1,2,4-triazole, transition metal salt and a mixed solvent system in a reaction container to react at a temperature higher than a solvent boiling point, and obtaining the corresponding bi-di triazole macrocyclic metal complex, wherein transient metal salt is FeCl2.4H2O, CoC12.6H2O, Ni(AC)2.4H2O or NiCl2.6H2O, the mixed solvent system is dichloromethane and a composition which is one or more selected from methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, petroleum ether and ethyl acetate. It is found by the applicant that the bi-di triazole macrocyclic metal complex can synthesize chiral sulfoxide through catalysis of asymmetrical oxidation of thioether.

Description

Two-Lian triazole Macrocyclic metal complex and synthetic method thereof and application
Technical field
The present invention relates to nitrogenous Macrocyclic metal complex, be specifically related to two-Lian triazole Macrocyclic metal complex and synthetic method thereof and application.
Background technology
Research neighborhood involved by large ring coordination chemistry comprises the subjects such as coordination chemistry, structural chemistry, organic chemistry, biological chemistry and materials chemistry, is an important branch of coordination chemistry, is an emerging interdisciplinary science.
Unique physico-chemical property of Macrocyclic metal complex and special biological function thereof (as oxygen carrier performance, biocatalysis, active etc. with protein-interacting, nucleic acid nicking activity, bacteriostasis antibiosis) obtain and study widely in recent years.Because this kind of compounds is similar to the Macrocyclic metal complex that finds in organism (as oxyphorase and chlorophyll a, be porphyrin Macrocyclic metal complex), therefore, the synthesis of this compounds and characteristic are studied, biological function can be provided for information about.Current, most method of fractional steps that adopts synthesizes Macrocyclic metal complex, namely first synthesizes macrocyclic ligand, then builds macrocyclic complex with itself and reacting metal salt.But for kind method cost is higher, and the monomer synthesizing large ring is easily polymerized chaining, cannot close.
Had not yet to see with transition metal salt and 5,5-diaminostilbene H, 1H-3,3 '-bis--1,2,4-triazole carries out the relevant report that reaction in－situ obtains two-Lian triazole Macrocyclic metal complex.
Summary of the invention
The technical problem to be solved in the present invention is to provide a series of two-Lian triazole Macrocyclic metal complexes newly, and their synthetic method and application.
Two-Lian triazole Macrocyclic metal complex of the present invention, its chemical formula is:
[MLCl 2]
Wherein, M is Fe (II), Co (II) or Ni (II), L are diformazan basic ring connection-5,5-diaminostilbene H, 1H-3,3 '-bis--1,2,4-triazole.
The diformazan basic ring connection-5,5-diaminostilbene H, the 1H-3 that relate in technique scheme, 3 '-bis--1,2,4-triazole, its structural formula is shown below:
The present invention also provides the synthetic method of above-mentioned two-Lian triazole Macrocyclic metal complex, be specially: get 5,5-diaminostilbene H, 1H-3,3 '-bis--1,2,4-triazole, transition metal salt and mixed solvent system are placed in reaction vessel, react at higher than the temperature of solvent boiling point, namely obtain corresponding two-Lian triazole Macrocyclic metal complex; Wherein:
Described transition metal salt is FeCl 24H 2o, CoCl 26H 2o, Ni (AC) 24H 2o or NiCl 26H 2o;
Described mixed solvent system is methylene dichloride and one or more the composition be selected from methyl alcohol, ethanol, Virahol, acetone, sherwood oil and ethyl acetate.
In above-mentioned synthetic method, 5,5-involved diaminostilbene H, 1H-3, the structural formula of 3 '-bis--1,2,4-triazole is shown below, and the synthesis of this compound can with reference to existing document (AlexanderA.DippoldandThomasM. nitrogen-RichBis-1,2,4-triazoles-AComparativeStudyofStructuralandEnergeticPropertiesChemi stryAEuropeanJournal2012,18,16742-16753.) carry out.
The synthetic route of synthetic method of the present invention is as follows:
In above-mentioned synthetic method, in the composition of described mixed solvent system, the volume ratio that methylene dichloride accounts in mixed solvent system should be more than or equal to 12%, and the composition of other solvent can be any proportioning meeting under mixed solvent system is the condition of 100%; Preferably, the volume ratio that methylene dichloride accounts in mixed solvent system is 15-30%.
In above-mentioned synthetic method, reaction is preferably carried out under 100-160 DEG C of condition, is more preferably and carries out under 120-160 DEG C of condition.
In above-mentioned synthetic method, the time of reaction is determined as required.Under normal circumstances, the reaction times just has target product to generate being equal to or greater than 1h, preferably controls the time of reaction for being more than or equal to 2h, and the time preferably controlling reaction further, the time more preferably controlling to react was 36-72h in order to be more than or equal to 12h.When reaction is carried out under 120-160 DEG C of condition, and the time controling of reaction is when 36-72h, and the productive rate of target product can reach 75-95%.
In synthetic method of the present invention, normally carry out temperature reaction again by after reaction raw materials stirring and dissolving.After completion of the reaction, be cooled to room temperature, then reactant filtered, collect crystal and be target product.Usual employing methyl alcohol, ethanol or Virahol wash crystal.
In synthetic method of the present invention, described reaction vessel should be the container that can bear certain pressure and temperature, can be specifically hydrothermal reaction kettle, closed low pressure horminess glass tube or closed vial.Described 5,5-diaminostilbene H, 1H-3, the amount ratio of 3 '-bis--1,2,4-triazole and transition metal salt is stoichiometric ratio, and the ratio of their amount of substance is 1:1-5 usually.The consumption of mixed solvent system is determined as required, under normal circumstances, when 5,5-diaminostilbene H, 1H-3,3 '-bis--1, when the consumption of 2,4-triazole and transition metal salt is respectively 0.3mmol and 0.6mmol, the amount ranges of mixed solvent system is 10 ~ 25mL.
The present invention also comprises the asymmetric oxidation of above-mentioned two-Lian triazole Macrocyclic metal complex at catalysis thioether with the application in synthesis of chiral sulfoxide.More particularly, be that the asymmetric oxidation of two-Lian triazole Macrocyclic metal complex at catalysis aminomethyl phenyl thioether is with the application in synthesis of chiral methyl phenyl sulfoxide.
Compared with prior art, feature of the present invention is:
1, two-Lian triazole Macrocyclic metal complexes of a series of novel structure are provided, and their synthetic method and application.
2, the present invention adopts original position template method to synthesize two-Lian triazole Macrocyclic metal complex, and cost is lower, and by product is few, has good economy;
3, two-Lian triazole Macrocyclic metal complex of the present invention has good stability, and more deep interaction can be had with biomacromolecule (as BSA), contribute to such title complex and carry out deep exploitation using forms such as albumen medicine carryings as newtype drug;
4, two-Lian triazole Macrocyclic metal complex of the present invention the asymmetric oxidation of catalysis aminomethyl phenyl thioether can obtain chirality methyl phenylsulfone with synthesis.
Accompanying drawing explanation
Fig. 1 is the coordination environment figure of title complex 1, title complex 2 and the title complex 3 that embodiment of the present invention 1-3 obtains, wherein Fig. 1 (a) coordination environment figure that is title complex 1, the coordination environment figure that the coordination environment figure that Fig. 1 (b) is title complex 2, Fig. 1 (c) are title complex 3;
Fig. 2 is the crystal accumulation figure of title complex 1, title complex 2 and the title complex 3 that embodiment of the present invention 1-3 obtains, wherein Fig. 2 (a) crystal accumulation figure that is title complex 1, the crystal accumulation figure that the crystal accumulation figure that Fig. 2 (b) is title complex 2, Fig. 2 (c) are title complex 3;
Fig. 3 is the powder diffraction pattern of title complex 1, title complex 2 and the title complex 3 that embodiment of the present invention 1-3 obtains, wherein Fig. 3 (a) is the powder diffraction pattern of title complex 1, Fig. 3 (b) is the powder diffraction pattern of title complex 2, and Fig. 3 (c) is the powder diffraction pattern of title complex 3;
Fig. 4 is the thermogravimetric curve of title complex 1, title complex 2 and the title complex 3 that embodiment of the present invention 1-3 obtains, and wherein curve 1 represents title complex 1, and curve 2 represents title complex 2, and curve 3 represents title complex 3;
Fig. 5 is obtained title complex 1, title complex 2 and the title complex 3 of embodiment of the present invention 1-3 and the interactional ultraviolet spectrogram of BSA, wherein Fig. 5 (a) be different concns title complex 1 and interactional ultraviolet spectrogram of BSA, in this figure, curve a to f is from top to bottom respectively concentration is 0,1,2,3,4 and 5 × 10 -6molL -1title complex 1 and 5.0 × 10 -7molL -1the interactional ultraviolet spectrogram of BSA; Title complex that Fig. 5 (b) is different concns 2 and the interactional ultraviolet spectrogram of BSA, in this figure, curve a to f is from top to bottom respectively concentration is 0,1,2,3,4 and 5 × 10 -6molL -1title complex 2 and 5.0 × 10 -7molL -1the interactional ultraviolet spectrogram of BSA; Title complex that Fig. 5 (c) is different concns 3 and the interactional ultraviolet spectrogram of BSA, in this figure, curve a to f is from top to bottom respectively concentration is 0,1,2,3,4 and 5 × 10 -6molL -1title complex 3 and 5.0 × 10 -7molL -1the interactional ultraviolet spectrogram of BSA;
Fig. 6 is the quenching of fluorescence figure interactional with BSA of title complex 1, title complex 2 and the title complex 3 that embodiment of the present invention 1-3 obtains, wherein Fig. 6 (a) be different concns title complex 1 and interactional quenching of fluorescence figure of BSA, in this figure, curve a to j is from top to bottom respectively concentration is 0,1,2,3,4,5,6,7,8 and 9 × 10 -6molL -1title complex 1 and 5.0 × 10 -7molL -1the interactional quenching of fluorescence figure of BSA; Title complex that Fig. 6 (b) is different concns 2 and the interactional quenching of fluorescence figure of BSA, in this figure, curve a to j is from top to bottom respectively concentration is 0,1,2,3,4,5,6,7,8 and 9 × 10 -6molL -1title complex 2 and 5.0 × 10 -7molL -1the interactional quenching of fluorescence figure of BSA; Title complex that Fig. 6 (c) is different concns 3 and the interactional quenching of fluorescence figure of BSA, in this figure, curve a to j is from top to bottom respectively concentration is 0,1,2,3,4,5,6,7,8 and 9 × 10 -6molL -1title complex 3 and 5.0 × 10 -7molL -1the interactional quenching of fluorescence figure of BSA;
Fig. 7 be obtained title complex 1, title complex 2 and the title complex 3 of embodiment of the present invention 1-3 at aminomethyl phenyl thioether through catalytic oxidation Quality Research, wherein Fig. 7 (a) is methyl phenyl sulfoxide 1h nmr spectrum; 7 (b), 7 (c), 7 (d) are respectively title complex 1, title complex 2 and the title complex 3 HPLC analysis of spectra as the methyl phenyl sulfoxide catalytic result of catalyzer.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and to understand content of the present invention better, but the present invention is not limited to following examples.
5, the 5-diaminostilbene H related in following embodiment, 1H-3,3 '-bis--1,2,4-triazole (hereinafter referred to as DABT), by document (AlexanderA.DippoldandThomasM. nitrogen-RichBis-1,2,4-triazoles-AComparativeStudyofStructuralandEnergeticPropertiesChemi stryAEuropeanJournal2012,18,16742-16753.) in method synthesize:
Commercially available concentrated hydrochloric acid (60 milliliters) is added in the oxalic acid (20.0g) and carbonic acid aminoguanidine (45.4g) of mixing.Reaction is reacted 1 hour under 70 degrees Celsius, produces a large amount of white solid, is collected by this solid vacuum filtration, and cleans with 240 ml distilled waters, and gained solid is starting compound DABT.
Embodiment 1: the synthesis of title complex 1
Take DABT (0.3mmol, 49.8g) and FeCl 24H 2o (0.6mmol, 119.2mg), joins by 5mLCH 3oH and 5mLCH 2cl 2in the mixed solvent of composition, stirring at normal temperature moves into band and moves in hydrothermal reaction kettle (polytetrafluoroethylsubstrate substrate, volume is 23 milliliters) after 30 minutes, be heated to 120 DEG C and insulation reaction 36 hours, then stopped reaction be down to room temperature, filters, obtains brown bulk crystals by methanol wash.Productive rate 75%.
Embodiment 2: the synthesis of title complex 2
Take DABT (0.3mmol, 49.8g) and CoCl 26H 2o (1mmol, 237.9mg), joins by 5mLCH 3oH and 5mLCH 2cl 2in the mixed solvent of composition, stirring at normal temperature moves into band and moves into hydrothermal reaction kettle (polytetrafluoroethylsubstrate substrate after 20 minutes, volume is 23 milliliters) in, be heated to 140 DEG C and keep 72 hours, then be down to room temperature with the gradient of 10 DEG C per hour, filter and obtain blue bulk crystals by methanol wash.Productive rate 80%.
Embodiment 3: the synthesis of title complex 3
Take DABT (0.3mmol, 49.8g) and Ni (AC) 24H 2o (0.3mmol, 74.7mg), joins by 5mLCH 3oH and 5mLCH 2cl 2in the mixed solvent of composition, stirring at normal temperature moves into band and moves into hydrothermal reaction kettle (polytetrafluoroethylsubstrate substrate after 10 minutes, volume is 23 milliliters) in, be heated to 160 DEG C and keep 72 hours, then be down to room temperature with the gradient of 10 DEG C per hour, filter and obtain green bulk crystals by methanol wash.Productive rate 95%.
Embodiment 4: the synthesis of title complex 3
Repeat embodiment 3, unlike:
(1) with the NiCl of equal amount of substance 26H 2o replaces Ni (AC) 24H 2o;
(2) mixed solvent is by 10mLCH 3cH 2oH and 5mLCH 2cl 2composition.
Reactant obtains green bulk crystals by methanol wash after filtering.Productive rate 41%.
Embodiment 5: the synthesis of title complex 2
Repeat embodiment 2, unlike:
(1) mixed solvent is made up of 10mL Virahol and 5mL methylene dichloride;
(2) temperature of reaction is 100 DEG C, and the reaction times is 2 hours.
Reactant obtains blue bulk crystals by methanol wash after filtering.Productive rate 44%.
Embodiment 6: the synthesis of title complex 1
Repeat embodiment 1, unlike:
(1) mixed solvent is made up of 10mL ethyl acetate, 2mL acetone and 5mL methylene dichloride;
(2) temperature of reaction is 120 DEG C, and the reaction times is 10 hours.
Reactant obtains brown bulk crystals by methanol wash after filtering.Productive rate 52%.
The IR of the title complex 1 that embodiment 7: embodiment 1-3 obtains, title complex 2 and title complex 3 and monocrystalline X-ray analysis
The title complex 1 obtained to embodiment 1-3, title complex 2 and title complex 3 carry out IR and monocrystalline X-ray analysis, and (crystallographic data of each title complex and part bond distance bond angle are respectively as shown in following table 1-4, the coordination environment figure of title complex 1-3 as shown in Figure 2, the crystal accumulation figure of title complex 1-3 as shown in Figure 3), find ligand L (i.e. diformazan basic ring connection-5, 5-diaminostilbene H, 1H-3, 3 '-bis--1, 2, 4-triazole) there is methylene radical and be connected to form 18 rings by methylene radical, can obtain methylene radical by contrast experiment is derive from methylene dichloride molecule, to 5, 5-diaminostilbene H, 1H-3, 3 '-bis--1, 2, amino in 4-triazole has carried out replacing being formed.Carry out structural characterization and parsing to these three complex crystals, determine its structure cell and space structure, these crystal belong to homeomorphism, and to belong to rhombic system spacer be Pbcn.Title complex 1 unit cell parameters is: title complex 2 unit cell parameters is: title complex 3 unit cell parameters is: the asymmetric cell of title complex has a metal ion species, and four nitrogen-atoms in central metallic ions and macrocyclic ligand and two chlorine Atomic coordinates form octahedral coordination configuration.
Table 1: the crystallography test result of title complex 1-3
Table 2: the part bond distance of title complex 1 with bond angle (°)
Table 3: the part bond distance of title complex 2 with bond angle (°)
Table 4: the part bond distance of title complex 3 with bond angle (°)
Embodiment 8: to the X-ray powder diffraction analysis of title complex 1, title complex 2 and title complex 3 that embodiment 1-3 obtains
Title complex 1, title complex 2 and the title complex 3 obtained to embodiment 1-3 carries out X-ray powder diffraction analysis, and gained powder graphic representation is as shown in (a), (b), (c) in Fig. 3.Powder diffraction pattern shows that the method gained macrocyclic complex is pure phase, and product is single.
Embodiment 9: to the thermogravimetric analysis of title complex 1, title complex 2 and title complex 3 that embodiment 1-3 obtains
Fig. 4 be the title complex 1, title complex 2 and the title complex 3 that obtain of embodiment 1-3 thermogravimetric analysis figure.Thermogravimetric analysis shows that in the scope of temperature 25-1000 DEG C and temperature rise rate be 5 DEG C/min, and tests the thermostability of title complex 1-3 respectively under the environment of nitrogen atmosphere protection.As shown in Figure 3-4, title complex 1 is all very stable to 356 DEG C of title complexs from the beginning, and after heating temperatures is to 356 DEG C, the skeleton of title complex just starts to cave in, until 764 DEG C, finally remaining resistates may be Fe 2o 3(experimental value: 30.72%, theoretical value: 33.12%).Title complex 2 is also all very stable to 356 DEG C from the beginning, and after heating temperatures is to 356 DEG C, the skeleton of title complex just starts to cave in, until 764 DEG C, finally remaining resistates is possible be Co 2o 3(experimental value: 32.10%, theoretical value: 33.12%).Title complex 3 from all very stable to 247 DEG C of title complexs, start to cave at 247 DEG C, until 734 DEG C, last resistates may be Ni 2o 3(experimental value: 30.04%, theoretical value: 34.15%).Obviously, title complex 1-3 has excellent thermostability.
Embodiment 10: to title complex 1, title complex 2 and title complex 3 that embodiment 1-3 obtains and bovine serum albumin interact and test
1, uv-visible absorption spectra measures
3mL5.0 × 10 are added in the quartz colorimetric utensil of 1cm -7molL -1bSA solution, adds the PBS buffered soln of 3mL, adds a certain amount of 1.0 × 10 with microsyringe at every turn in corresponding reference quartz colorimetric utensil -6molL -1complex solution, scan the Zi Wai – visible absorption spectra of above-mentioned solution under room temperature.
2, Steady state fluorescence spectrum spectrometry
In the quartz colorimetric utensil of 1cm, add 3mL concentration is 5.0 × 10 -7molL -1bSA solution, adds a certain amount of 1.0 × 10 with microsyringe at every turn -6molL -1complex solution, fixing excitation wavelength is λ ex=280nm, slit is 5/5nm, and at the temperature of 298K, within the scope of scanning 290-450nm, the fluorescence spectrum of BSA and title complex are to the fluorescence quenching spectrum of BSA.
Experimental result
Title complex and the interactional uv-visible absorption spectra of BSA are as Fig. 5 (a), 5 (b), shown in 5 (c), as can be seen from the figure, the absorption peak that existence two is main in BSA molecule, wherein the charateristic avsorption band of peptide bond is positioned near 203nm, and the conformation with protein is relevant; And be positioned near 279nm from the charateristic avsorption band of the heterocycle conjugated double bond in tyrosine, tryptophane and phenylalanine residue.Can find from figure, add along with title complex is regular, the ultraviolet absorption curve of protein remains unchanged substantially, but be positioned at the absorption peak strength near 203nm all decrease under the existence of title complex and certain red shift occurs, and near 278nm, except the intensity enhancing that title complex 1 makes BSA absorption peak herein, other title complex all makes absorption peak strength herein reduce, this shows, all can there is combination in various degree in title complex and protein, this can cause the structure of protein to change, and BSA skeleton is opened up folding and loose.
Fig. 6 (a), 6 (b), 6 (c) is the fluorescence quenching spectrum of title complex to BSA, and as can be seen from the figure, when under 298K, excitation wavelength is 280nm, BSA has stronger fluorescence emission peak near 345nm.Keep BSA concentration constant, increase the concentration of title complex gradually, the fluorescence intensity regular decline all gradually of BSA can be found, and keep peak shape constant, show there occurs interaction between title complex and BSA thus cause BSA quenching of fluorescence.
As can be seen from the interaction result of above-mentioned title complex and BSA, title complex can be combined preferably with BSA, using the medicine carrying albumen of BSA as title complex if show, can effectively improve its bioavailability, have good patent medicine DEVELOPMENT PROSPECT.
Embodiment 11: to obtained title complex 1, title complex 2 and the title complex 3 of embodiment 1-3 in the qualitative test of aminomethyl phenyl thioether through catalytic oxidation.
According to document, the asymmetric oxidation reaction formula of aminomethyl phenyl thioether is as follows:
Under 25 DEG C of conditions, in 5ml penicillin bottle, add 0.01molL successively -1dichloromethane solution, aminomethyl phenyl thioether 0.53mmol, catalyzer (title complex 1,2,3) 0.265 μm of ol, constant temperature stirs and makes it abundant mixing in 5 hours, add hydrogen peroxidase 10 .795mmol again, final mixing solutions cumulative volume is 2ml, stirs 20 hours under constant temperature blender with magnetic force fixed rotating speed.Add excessive saturated Na 2sO 3solution makes reaction stop, and then uses a small amount of CH 2cl 2repeatedly extract, merge organic phase, and add a certain amount of anhydrous Na 2sO 4drying, carries out separation and purification by column chromatography to product, and eluent is sherwood oil: ethyl acetate=1:3.Vacuum rotary steam, can obtain product.
Experimental result
After getting a certain amount of separation and purification, products therefrom carries out HNMR (300Hz, CDC1 3) analyze, spectrogram is as Fig. 7 (a).Chemical shift δ H1=2.74 (t in figure, 3H) be the hydrogen on methyl, δ H2=7.27-7.67 (m, 5H) be benzene ring hydrogen in methyl phenyl sulfoxide, δ=7.26 are solution peak, and its integration, than being δ H2: δ H1=5:3, also can show that the number of hydrogen in compound is 8 thus, conform to product, thus the product synthesized by proving is methyl phenyl sulfoxide.
The a small amount of Virahol of product separation and purification obtained dissolves, and being made into concentration is 1.0 × 10 -3molL -1solution, then use the enantiomorph of high-performance liquid chromatogram determination product, as Fig. 7 (b), 7 (c), 7 (d).
Table 5: the correlation parameter of high-efficient liquid phase chromatogram
The HPLC condition of methyl phenyl sulfoxide raceme is: ChiralcolumnOB-H (4.6 Φ mm × 250mm) post, moving phase normal hexane and Virahol volume ratio are 4:1, flow velocity is 0.8ml/min, UV:254nm, peak sequence: S type (about 13min), R type (about 22min).Enantio-selectivity formula is:
e . e % = [ R ] - [ S ] [ R ] + [ S ] 100 % - - - ( 4 - 5 )
As calculated, the productive rate of each title complex and hybrid protein and ee value list in table 6.
Table 6: title complex 1,2, the productive rate of 3 catalysis gained methyl phenyl sulfoxide and ee value

Claims (9)

1. pair-Lian triazole Macrocyclic metal complex, its chemical formula is:
[MLCl 2]
Wherein, M is Fe (II), Co (II) or Ni (II), L are diformazan basic ring connection-5,5-diaminostilbene H, 1H-3,3 '-bis--1,2,4-triazole.
2. the synthetic method of two-Lian triazole Macrocyclic metal complex according to claim 1, it is characterized in that: get 5,5-diaminostilbene H, 1H-3,3 '-bis--1,2,4-triazole, transition metal salt and mixed solvent system are placed in reaction vessel, react at higher than the temperature of solvent boiling point, namely obtain corresponding two-Lian triazole Macrocyclic metal complex; Wherein:
Described transition metal salt is FeCl 24H 2o, CoCl 26H 2o, Ni (AC) 24H 2o or NiCl 26H 2o;
Described mixed solvent system is methylene dichloride and one or more the composition be selected from methyl alcohol, ethanol, Virahol, acetone, sherwood oil and ethyl acetate.
3. synthetic method according to claim 2, is characterized in that: in the composition of mixed solvent system, and the volume ratio that methylene dichloride accounts in mixed solvent system is 12-30%.
4. the synthetic method according to Claims 2 or 3, is characterized in that: react and carry out under 100-160 DEG C of condition.
5. the synthetic method according to Claims 2 or 3, is characterized in that: react and carry out under 120-160 DEG C of condition.
6. the synthetic method according to Claims 2 or 3, is characterized in that: the time of reaction is for being more than or equal to 1h.
7. the synthetic method according to Claims 2 or 3, is characterized in that: the time of reaction is for being more than or equal to 12h.
8. two-Lian triazole Macrocyclic metal complex according to claim 1 at the asymmetric oxidation of catalysis thioether with the application in synthesis of chiral sulfoxide.
9. application according to claim 8, is characterized in that: two-Lian triazole Macrocyclic metal complex according to claim 1 at the asymmetric oxidation of catalysis aminomethyl phenyl thioether with the application in synthesis of chiral methyl phenyl sulfoxide.
CN201510670263.8A 2015-10-16 2015-10-16 Bi-di triazole macrocyclic metal complex and synthesizing method and application thereof Pending CN105237580A (en)

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CN105879914A (en) * 2016-06-03 2016-08-24 湖南师范大学 Temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst and preparation method thereof
CN105879914B (en) * 2016-06-03 2018-03-30 湖南师范大学 A kind of temperature sensitive type ionic liquid chirality Salen Ti composition catalysts and preparation method thereof
CN109912628A (en) * 2019-04-22 2019-06-21 广西师范大学 A kind of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage and its in-situ synthetic method
CN109970767A (en) * 2019-04-22 2019-07-05 广西师范大学 The four of a kind of sulfur-bearing-sulfide linkage gather big ring trinuclear iron complex and its in-situ synthetic method

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