CN105859786A - 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) 5-methylisophthalic acid manganese complex single crystal and application - Google Patents

1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) 5-methylisophthalic acid manganese complex single crystal and application Download PDF

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CN105859786A
CN105859786A CN201610255844.XA CN201610255844A CN105859786A CN 105859786 A CN105859786 A CN 105859786A CN 201610255844 A CN201610255844 A CN 201610255844A CN 105859786 A CN105859786 A CN 105859786A
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dimethyl
mipt
dmac
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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) 5-methylisophthalic acid manganese complex single crystal and a preparation method and application thereof. A structure is [Mn(L)0.5(mipt)(DMAC)], wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazole-1-yl)phenyl)-1H-1,2,4-triazole; mipt=5-methylisophthalic acid; DMAC=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, mipt and MnCl2 4H2O in a mixture of water and DMAC 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:mipt:MnCl2 4H2O 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) 5-methylisophthalic acid manganese complex single crystal special for fluorophenylboronic acid to generate a 4,4'-difluorobiphenyl catalyst.

Description

The double triazole oreinol dioctyl phthalate manganese of 1,4-dimethyl-2,5-two-1H-1,2,4- Complex monocrystal and 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 Azoles oreinol dioctyl phthalate manganese complex monocrystalline [Mn (L)0.5(mipt) (DMAC)] preparation method and as catalyst aspect Application, wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yls) phenyl)-1H-1,2,4-triazoles；mipt =oreinol dioctyl phthalate, DMAC=N, N'-dimethyl acetylamide.
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, mipt and MnCl2·4H2After O stirs half an hour in water and DMAC Filtering, filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks, structure is [Mn (L)0.5 (mipt) (DMAC)], wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yls) phenyl)-1H-1,2,4-tri- Azoles；Mipt=oreinol dioctyl phthalate；DMAC=N, N'-dimethyl acetylamide.This complex monocrystal 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 oreinol dioctyl phthalate manganese complexes, it is special Levy and be that this mono-crystalline structures uses APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha ray, 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 single crystal data from difference Fourier electron density map:
Its structure is as follows:
[Mn(L)0.5(mipt) (DMAC)], wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Mipt=oreinol dioctyl phthalate；DMAC=N, N'-dimethyl acetylamide.
The present invention further discloses the double triazole oreinol dioctyl phthalate manganese of 1,4-dimethyl-2,5-two-1H-1,2,4- The preparation method of complex monocrystal, it is characterised in that it is to use room temperature volatility process, by L, mipt and MnCl2·4H2O at water and Filtering after stirring half an hour in DMAC, filtrate room temperature obtains after volatilizing two weeks being suitable for the colourless block brilliant of X-ray single crystal diffraction Body；Wherein L:mipt:MnCl2·4H2The mol ratio of O is 1:1:1；
The structure of the double triazole oreinol dioctyl phthalate manganese complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-is [Mn (L)0.5(mipt)(DMAC)]；Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2, 4-triazole；Mipt=oreinol dioctyl phthalate；DMAC=N, N'-dimethyl acetylamide；
L mipt。
The present invention further discloses the double triazole oreinol dioctyl phthalate of 1,4-dimethyl-2,5-two-1H-1,2,4- Manganese complex monocrystalline specificity generates 4 to fluorobenzoic boric acid, and 4'-DfBP catalyst 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 oreinol dioctyl phthalate manganese of a kind of 1,4-dimethyl-2,5-two-1H-1,2,4-disclosed by the invention is joined Compound monocrystalline have the advantage that 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) the double triazole oreinol dioctyl phthalate manganese of the 1,4-dimethyl-2,5-two-1H-1,2,4-prepared by the present invention coordinates Thing monocrystalline, production cost is low, and method is easy, is suitable for large-scale production, in catalysis, fluorobenzoic boric acid is generated 4,4'-DfBP side Mask has good catalytic effect.
Accompanying drawing explanation
The crystal structure figure of Fig. 1: complex monocrystal；
The two-dimensional structure figure 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 DMF.Start stirring 100oC, reacts 24 hours.Reaction After end, 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, yield 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), 5- Methylresorcinol dioctyl phthalate (mipt) (0.1 mmol) and MnCl2·4H2O (0.1 mmol) is at water (10 mL) and DMAC (2 ML) filtering after stirring half an hour in mixed solvent, filtrate room temperature obtains being suitable for the nothing of X-ray single crystal diffraction after volatilizing two weeks Color bulk crystals.Productivity: 40%.Elementary analysis (C38H42Mn2N8O10) theoretical value (%): C, 51.83；H, 4.81；N, 12.72.Real Measured value: C, 51.36；H, 4.85；N, 12.64.
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, Utilize software 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: fluorobenzoic boric acid (0.82 mmol) and cesium carbonate (0.01 g) are dissolved in 3 mL DMF by replacement, add 5 mg Catalyst, stirs 5 hours under room temperature, CH2Cl2Extraction, washing, it is dried, filters, precipitation, thick product is through petrol ether/ethyl acetate Mixed liquor (v:v=1:1) by silica gel chromatography post affords product.
Result: obtaining 4,4'-DfBP 0.0748 g, calculated catalysis productivity is 96%.
Embodiment 5
Conclusion:
(1) the double triazole oreinol dioctyl phthalate manganese complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-is for catalysis Substrate 1-naphthalene phenylboric acid does not play any catalytic action.
(2) the double triazole oreinol dioctyl phthalate manganese complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-for 3-methoxyphenylboronic acid, 4-methylthio phenyl boric acid, 4-chlorophenylboronic acid, 4-pyridine phenylboric acid catalytic effect general, be catalyzed productivity Between 4-17%.
(3) the double triazole oreinol dioctyl phthalate manganese complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-for The catalytic effect of catalytic substrate 4-fluorobenzoic boric acid is best, and catalysis productivity is up to 96%.
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 oreinol dioctyl phthalate manganese complexes, its It is characterised by that this mono-crystalline structures uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, 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 single crystal data from difference Fourier electron density map:
Its structure is as follows:
[Mn(L)0.5(mipt) (DMAC)], wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Mipt=oreinol dioctyl phthalate；
DMAC=N, N'-dimethyl acetylamide.
2. the double triazole oreinol dioctyl phthalate manganese complex of 1,4-dimethyl-2,5-two-1H-1,2,4-described in claim 1 The preparation method of monocrystalline, it is characterised in that it is to use room temperature volatility process, L, mipt and MnCl2·4H2O stirs in water and DMAC Filtering after mixing half an hour, filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks；Wherein L: mipt:MnCl2·4H2The mol ratio of O is 1:1:1；
The structure of the double triazole oreinol dioctyl phthalate manganese complex monocrystalline of 1,4-dimethyl-2,5-two-1H-1,2,4-is [Mn (L)0.5(mipt)(DMAC)]；Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2, 4-triazole；Mipt=oreinol dioctyl phthalate；DMAC=N, N'-dimethyl acetylamide；
L mipt。
3. the double triazole oreinol dioctyl phthalate manganese complex of 1,4-dimethyl-2,5-two-1H-1,2,4-described in claim 1 Monocrystalline specificity generates the application in terms of 4,4'-DfBP catalyst to fluorobenzoic boric acid.
CN201610255844.XA 2016-04-25 2016-04-25 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) 5-methylisophthalic acid manganese complex single crystal and application Pending CN105859786A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105418657A (en) * 2016-01-05 2016-03-23 天津师范大学 1,4-dimethyl-2,5-dimethylene bis(triazole)isophthalic acid-included dimethylacetamide cadimium complex single crystal and application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105418657A (en) * 2016-01-05 2016-03-23 天津师范大学 1,4-dimethyl-2,5-dimethylene bis(triazole)isophthalic acid-included dimethylacetamide cadimium complex single crystal and application

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