CN105732668A - 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole copper mixed complex single crystal and application - Google Patents

1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole copper mixed complex single crystal and application Download PDF

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CN105732668A
CN105732668A CN201610255175.6A CN201610255175A CN105732668A CN 105732668 A CN105732668 A CN 105732668A CN 201610255175 A CN201610255175 A CN 201610255175A CN 105732668 A CN105732668 A CN 105732668A
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dimethyl
mipt
dmac
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triazole
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王中良
王英
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Tianjin University
Tianjin Normal University
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    • 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 System
    • 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
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • 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

Abstract

The invention discloses a 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole m-methyl isophthalic acid copper mixed complex single crystal and a preparation method and application thereof. The structure of the single crystal is {[Cu(L)(mipt)(H2O)]DMAC.H2O}, wherein L is equal to 1-(2,5-dimethyl-4(1H-1,2,4-triazole-1-yl)phenyl)-1H-1,2,4-triazole; mipt is equal to m-methyl isophthalic acid; DMAC is equal to N,N'-dimethylacetamide. The invention further discloses the preparation method of the single crystal. According to the preparation method, a normal temperature volatilization method is adopted, that is, L, mipt and CuCl2.4H2O are stirred in water and DMAC for half an hour before being filtered, filtrate is volatilized at normal temperature for two weeks, and then the colorless bulk crystal suitable for X-ray single crystal diffraction is obtained, wherein the molar ratio of L to mipt to CuCl2.4H2O is 1:1:1. The invention further discloses the specific application of the 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole m-methyl isophthalic acid copper complex single crystal to a catalyst for generation of 4,4'-difluorobiphenyl from p-fluorophenylboronic acid.

Description

The double triazole copper mixed ligand coordination compound 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 Methylresorcinol dioctyl phthalate copper complex monocrystalline { [Cu (L) (mipt) (H between azoles2O)]·DMAC·H2The preparation method of O} and conduct Application in terms of catalyst, wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yls) phenyl)-1H-1,2,4- Triazole；A mipt=methylresorcinol 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 CuCl2·4H2After 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 { [Cu (L) (mipt)(H2O)]·DMAC·H2O}, wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yls) phenyl)- 1H-1,2,4-triazole；A mipt=methylresorcinol dioctyl phthalate；DMAC=N, N'-dimethyl acetylamide.This coordination compound also can be made Applied for fluorobenzoic boric acid being generated the catalyst of 4,4'-DfBP.
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 methylresorcinol dioctyl phthalate copper complex between 2,4-double triazoles, 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:
{[Cu(L)(mipt)(H2O)]·DMAC·H2O}, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
A mipt=methylresorcinol dioctyl phthalate；DMAC=N, N'-dimethyl acetylamide.
The present invention further discloses methylresorcinol dioctyl phthalate copper between 1,4-dimethyl-2,5-two-1H-1,2,4-double triazole The preparation method of complex monocrystal, it is characterised in that it is to use room temperature volatility process, by L, mipt and CuCl2·4H2O 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:CuCl2·4H2The mol ratio of O is 1:1:1；
Between 1,4-dimethyl-2,5-two-1H-1,2,4-double triazole, the structure of methylresorcinol dioctyl phthalate copper complex monocrystalline is { [Cu (L)(mipt)(H2O)]·DMAC·H2O}；Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)- 1H-1,2,4-triazole；A mipt=methylresorcinol dioctyl phthalate；DMAC=N, N'-dimethyl acetylamide;
L mipt。
The present invention further discloses methylresorcinol dioctyl phthalate between 1,4-dimethyl-2,5-two-1H-1,2,4-double triazole Copper complex monocrystalline 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.
Between the double triazole of a kind of 1,4-dimethyl-2,5-two-1H-1,2,4-disclosed by the invention, methylresorcinol dioctyl phthalate copper 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) methylresorcinol dioctyl phthalate copper between the double triazole of the 1,4-dimethyl-2,5-two-1H-1,2,4-prepared by the present invention Complex monocrystal, production cost is low, and method is easy, is suitable for large-scale production.In catalysis, fluorobenzoic boric acid is generated 4,4'-difluoro to join Benzene aspect 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), Methylresorcinol dioctyl phthalate (mipt) (0.1 mmol) and CuCl2·4H2O (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 (C25H32CuN7O7) theoretical value (%): C, 49.54；H, 5.32；N, 16.18.Real Measured value: C, 49.45；H, 5.35；N, 16.04.
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: 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) between 1,4-dimethyl-2,5-two-1H-1,2,4-double triazole methylresorcinol dioctyl phthalate copper complex for catalytic substrate 1-naphthalene phenylboric acid and 3-methoxyphenylboronic acid do not play any catalytic action.
(2) between 1,4-dimethyl-2,5-two-1H-1,2,4-double triazole methylresorcinol dioctyl phthalate copper complex for 4-first Sulfenyl phenylboric acid, 4-chlorophenylboronic acid, 4-pyridine phenylboric acid catalytic effect general, catalysis productivity is between 4-17%.
(3) between 1,4-dimethyl-2,5-two-1H-1,2,4-double triazole methylresorcinol dioctyl phthalate copper complex for catalysis The catalytic effect of 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 methylresorcinol dioctyl phthalate copper complex between 2,4-double triazoles, 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:
{[Cu(L)(mipt)(H2O)]·DMAC·H2O}, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
A mipt=methylresorcinol dioctyl phthalate；DMAC=N, N'-dimethyl acetylamide.
2. methylresorcinol dioctyl phthalate copper complex between the double triazole 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 CuCl2·4H2O 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:CuCl2·4H2The mol ratio of O is 1:1:1；
Between 1,4-dimethyl-2,5-two-1H-1,2,4-double triazole, the structure of methylresorcinol dioctyl phthalate copper complex monocrystalline is { [Cu (L)(mipt)(H2O)]·DMAC·H2O}；Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)- 1H-1,2,4-triazole；A mipt=methylresorcinol dioctyl phthalate；DMAC=N, N'-dimethyl acetylamide；
L mipt。
3. methylresorcinol dioctyl phthalate copper complex between the double triazole of 1,4-dimethyl-2,5-two-1H-1,2,4-described in claim 1 Monocrystalline specificity generates the application in terms of the catalyst of 4,4'-DfBP to fluorobenzoic boric acid.
CN201610255175.6A 2016-04-25 2016-04-25 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole copper mixed complex single crystal and application Pending CN105732668A (en)

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Application publication date: 20160706