CN105859753A - 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) three-dimensional zinc complex single crystal and application - Google Patents

1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) three-dimensional zinc complex single crystal and application Download PDF

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CN105859753A
CN105859753A CN201610255182.6A CN201610255182A CN105859753A CN 105859753 A CN105859753 A CN 105859753A CN 201610255182 A CN201610255182 A CN 201610255182A CN 105859753 A CN105859753 A CN 105859753A
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dimethyl
tpa
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王中良
王英
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Tianjin University
Tianjin Normal University
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Abstract

The invention discloses a 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) three-dimensional zinc complex single crystal and a preparation method and an application thereof. A structure is [Zn(L)(tpa)] 1.5DEAC, wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazole-1-yl)phenyl)-1H-1,2,4-triazole; tpa=terephthalic acid; DEAC=N,N'-dimethylacetamide. The invention also discloses the preparation method of the single crystal. The preparation method is a normal-temperature volatilizing method, comprising the following steps of stirring L, tpa and Zn(NO3)2 6H2O in a mixed solvent of water and DEAC for 0.5h, filtering, and volatilizing a filtrate for two weeks at the normal temperature, so as to obtain the colorless blocky crystal which is suitable for X-ray single crystal diffraction, wherein the molar ratio of L:tpa:Zn(NO3)2 6H2O is 1:1:1. The invention further discloses the application of the 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) three-dimensional zinc complex single crystal special for fluorophenylboronic acid to generate a 4,4'-difluorobiphenyl catalyst.

Description

The double triazole three-dimensional Zn complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-with Application
The present invention obtains the subsidy of Tianjin innovation team of Education Commission (TD12-5037).
Technical field
The invention belongs to organic and Inorganic synthese technical field, relate to Isosorbide-5-Nitrae-dimethyl-2,5-bis--1H-1,2,4-double three The preparation method of azoles three-dimensional Zn complex monocrystalline [Zn (L) (tpa)] 1.5DEAC and as the application in terms of catalyst, wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；Tpa=p-phthalic acid； DEAC=N, N'-diethyl acetamide.
Background technology
1,2,4-triazole and derivant thereof have the coordination feature of pyrazoles and imidazoles concurrently, are that the bridging that coordination ability is stronger is joined Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound the most.These parts can be former with the nitrogen on 1,2 Son forms N1, N2-bridging pattern with metallic ion coordination, can be by 2,4 for 4 unsubstituted 1,2,4-triazole derivatives 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 dimension Metal complex has been the vital step of device.
The present invention is i.e. to use room temperature volatility process, i.e. L, tpa and Zn (NO3)2·6H2O is in the mixed solvent of water and DEAC Stirring is filtered after half an hour, and filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction, structure after volatilizing two weeks For [Zn (L) (tpa)] 1.5DEAC, wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yls) phenyl)- 1H-1,2,4-triazole；Tpa=p-phthalic acid；DEAC=N, N'-diethyl acetamide.This coordination compound is alternatively arranged as fluorine Phenylboric acid generates the catalyst of 4,4'-DfBP and is applied.
Summary of the invention
Following technical scheme is current inventor provides for this:
A kind of Isosorbide-5-Nitrae-dimethyl-2,5-bis--1H-1, the monocrystalline of 2,4-double triazole three-dimensional Zn complexes, it is characterised in that this monocrystalline Structure uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, and λ=0.71073 is for entering Penetrate radiation, collect point diffraction with ω-2 θ scan mode, obtain cell parameter through least square refinement, from difference Fourier Electron density map utilizes software to solve single crystal data:
Its structure is as follows:
[Zn (L) (tpa)] 1.5DEAC, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Tpa=p-phthalic acid；
DEAC=N, N'-diethyl acetamide.
The present invention further discloses the double triazole three-dimensional Zn complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4- Preparation method, it is characterised in that it is to use room temperature volatility process, by L, tpa and Zn (NO3)2·6H2O is in water and the mixing of DEAC Filtering after stirring half an hour in solvent, filtrate room temperature obtains after volatilizing two weeks being suitable for the colourless block brilliant of X-ray single crystal diffraction Body；Wherein L:tpa:Zn (NO3)2·6H2The mol ratio of O is 1:1:1；
The structure of the double triazole three-dimensional Zn complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-is [Zn (L) (tpa)] 1.5DEAC；Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；tpa = P-phthalic acid；DEAC=N, N'-diethyl acetamide；
L tpa。
The present invention further discloses the double triazole three-dimensional Zn complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4- Specificity generates 4 to fluorobenzoic boric acid, and the catalyst of 4'-DfBP is applied, and experimental result shows:
(1) catalyst that the complex monocrystal specificity in embodiment 2 generates 4,4'-DfBP to fluorobenzoic boric acid has relatively Good catalytic effect, catalysis productivity reaches 96%；
(2) complex monocrystal is to 3-methoxyphenylboronic acid, 1-naphthalene phenylboric acid, 4-methylthio phenyl boric acid, 4-chlorophenylboronic acid, 4-pyrrole Pyridine phenylboric acid catalytic effect does not the most even react.
The double triazole three-dimensional Zn complex monocrystalline of a kind of 1,4-dimethyl-2,5-two-1H-1,2,4-disclosed by the invention is had Some advantages and feature are:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) Isosorbide-5-Nitrae-dimethyl-2 prepared by the present invention, 5-bis--1H-1,2,4-double triazole three-dimensional Zn complex monocrystalline, Production cost is low, and method is easy, is suitable for large-scale production.Have in terms of catalysis generates 4,4'-DfBP to fluorobenzoic boric acid Good catalytic effect.
Accompanying drawing explanation
The crystal structure figure of Fig. 1: complex monocrystal；
The tomograph of Fig. 2: complex monocrystal；
Fig. 3: 4,4'-DfBP1H NMR schemes.
Detailed description of the invention
Below in conjunction with 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.Raw materials used it is commercially available.All raw materials are all public from chemical reagent both domestic and external The raw materials such as department buys, such as Isosorbide-5-Nitrae-two bromo-2,5-dimethyl benzene, through continuation purification but directly do not use.
Embodiment 1
1,4-bis-bromo-2,5-dimethyl benzene: 1H-1,2,4-triazole: potassium carbonate: the mol ratio of copper oxide is 2:10:30:1
Be separately added in equipped with 50 mL three neck round bottom flasks of magneton, reflux condenser and thermometer CuO (0.0398 mg, 0.5 mmol), potassium carbonate (2.0731 g, 15 mmol), 1H-1,2,4-triazoles (0.345 mg, 5 mmol), Isosorbide-5-Nitrae-two Bromo-2,5-dimethyl benzene (0.3360 g, 1 mmol), 20 mL DEAC.Start stirring 100oC, reacts 24 hours.Instead After should terminating, reactant liquor being down to room temperature, filter, filtrate adds 100 mL water, separates out a large amount of precipitation, sucking filtration, collects filter cake, receives Rate 60%.Elementary analysis (C12N6H12) theoretical value (%): C, 59.99；H, 5.03；N, 34.98.Measured value: C, 60.02；H, 5.05；N, 35.05；
1,4-bis-bromo-2,5-dimethyl benzene 1H-1,2,4-triazole.
The bromo-2,5-dimethyl benzene of the preferred 1,4-of the present invention bis-: 1H-1,2,4-triazole: potassium carbonate: the mol ratio of copper oxide is 2:10:30:1；Reaction temperature 80-200 DEG C, 12-120 hour response time.Use " one kettle way ", by bromo-for Isosorbide-5-Nitrae-two 2,5-bis- Methylbenzene and 1H-1,2,4-triazoles prepare this organic compound in a heated condition, 1-(2,5-dimethyl-4-(1H-1,2,4- Triazol-1-yl) phenyl)-1H-1,2,4-triazole (L).
Embodiment 2
1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole (L) (0.1 mmol), right Phthalic acid (tpa) (0.1 mmol) and Zn (NO3)2·6H2O (0.1 mmol) is at water (10 mL) and DEAC (2 mL) Filtering after stirring half an hour in mixed solvent, filtrate room temperature obtains being suitable for the colourless bulk of X-ray single crystal diffraction after volatilizing two weeks Crystal.Productivity: 40%.Elementary analysis (C58H71N15O11Zn2) theoretical value (%): C, 54.21；H, 5.57；N, 16.35.Measured value: C, 54.28；H, 5.49；N, 16.32.
Embodiment 3
Crystal structure determination uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, and λ= 0.71073 is incident radiation, collects point diffraction with ω-2 θ scan mode, obtains cell parameter through least square refinement, Software is utilized to solve crystal structure from difference Fourier electron density map, and through Lorentz lorentz and polarity effect correction.All of H is former Son is synthesized by difference Fourier and determines through preferable position calculation.Detailed axonometry data:
Embodiment 4
Specificity is as the concrete instance of catalyst
Method: replacement be dissolved in fluorobenzoic boric acid (0.82 mmol) and cesium carbonate (0.01 g) in 3 mL DEAC, adds 5 Mg catalyst, stirs 5 hours under room temperature, CH2Cl2Extraction, washing, it is dried, filters, precipitation, thick product is through petroleum ether/acetic acid second Ester mixed liquor (v:v=1:1) by silica gel chromatography post affords product.
Result: obtaining 4,4'-DfBP 0.0764 g, calculated catalysis productivity is 98%.
Embodiment 5
Conclusion:
(1) the double triazole three-dimensional Zn complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-is for catalytic substrate 4-methyl mercapto Phenylboric acid does not play any catalytic action.
(2) the double triazole three-dimensional Zn complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-is for 3-methoxybenzene boron Acid, 1-naphthalene phenylboric acid, 4-chlorophenylboronic acid, 4-pyridine phenylboric acid are catalyzed hardly, and catalysis productivity is between 1-10%.
(3) the double triazole three-dimensional Zn complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-is for catalytic substrate 4-fluorine The catalytic effect of phenylboric acid is best, and catalysis productivity is up to 98%.
After the preferred embodiment described in detail, it is familiar with this skilled worker and is clearly understood that, without departing from above-mentioned Can carry out various change and amendment under claim and spirit, all technical spirit according to the present invention are to above example institute Any simple modification, equivalent variations and the modification made, belongs to the scope of technical solution of the present invention.And the present invention is not illustrated The restriction of example embodiment in book.

Claims (3)

1. Isosorbide-5-Nitrae-dimethyl-2,5-bis--1H-1, the monocrystalline of 2,4-double triazole three-dimensional Zn complexes, it is characterised in that this is single Crystal structure uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, and λ=0.71073 is Incident radiation, collects point diffraction with ω-2 θ scan mode, obtains cell parameter through least square refinement, from difference Fourier Leaf electron density map utilizes software to solve single crystal data:
Its structure is as follows:
[Zn (L) (tpa)] 1.5DEAC, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Tpa=p-phthalic acid；
DEAC=N, N'-diethyl acetamide.
2. the preparation side of the double triazole three-dimensional Zn complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-described in claim 1 Method, it is characterised in that it is to use room temperature volatility process, i.e. L, tpa and Zn (NO3)2·6H2O is in the mixed solvent of water and DEAC Stirring is filtered after half an hour, and filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks, wherein L:tpa:Zn(NO3)2·6H2The mol ratio of O is 1:1:1；
The structure of the double triazole three-dimensional Zn complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-is [Zn (L) (tpa)] 1.5DEAC；Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；tpa = P-phthalic acid；DEAC=N, N'-diethyl acetamide；
L tpa。
3. the double triazole three-dimensional Zn complex monocrystalline specificity pair of 1,4-dimethyl-2,5-two-1H-1,2,4-described in claim 1 Fluorobenzoic boric acid generates the application in terms of the catalyst of 4,4'-DfBP.
CN201610255182.6A 2016-04-25 2016-04-25 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) three-dimensional zinc complex single crystal and application Pending CN105859753A (en)

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CN104497018A (en) * 2014-12-15 2015-04-08 天津师范大学 Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex

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