CN103145763A - Novel cyclometal ligand-platinum complex and preparation method and application thereof - Google Patents
Novel cyclometal ligand-platinum complex and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a novel cyclometal ligand-platinum complex and a preparation method and application thereof, and belongs to the technical field of electronic materials. The novel cyclometal ligand-platinum complex is convenient in template design and easy to obtain. Triphenylaminyl, quinolyl and trifluoromethyl are introduced in a material, and the electron structure and the hole injection and transmission performance of the material can be conveniently adjusted by adjusting substituents on an aza heteroaromatic ring. The complex provided by the invention is good in thermal stability and hole injection and transmission performance, and has wide application prospect in the fields of organic electroluminescent materials, oxygen sensing materials, dyes and medicines and the like. The oxygen sensor prepared by the complex has the advantages of simple structure, low cost, reliable work and the like; and the complex can be prepared into a portable oxygen sensor to be popularized and used.
Description
Technical field
The present invention relates to a kind of Novel ring metal ligand-platinum complex and preparation method thereof and application, it belongs to technical field of electronic materials.
Background technology
Cyclic metal complexes-platinum complex has special rigidity condensed ring structure and the good characteristics such as hole transport performance, is widely used in organic photoelectrical material, oxygen sensor, dyestuff and medicine and other fields (Adv.Funct.Mater.2006,16,838 – 846; Eur.J.Inorg.Chem.2006,3676 – 3683).In recent years, electroluminescent organic material and device (OrganicLight-EmittingDiodes, OLEDs) have broad application prospects in technique of display of new generation, have caused the extensive concern of scientific circles and international renowned company and have played an active part in.The common technique of display of electroluminescent organic material and device and other is compared, and has and is convenient to design, and luminous efficiency is high, and the visual angle is wide, and fast response time is ultra-thin, light weight, and glow color can cover the advantages such as whole visible region.（Organometallics2010,29,3912-3921）。
Quinoline group and aromatic ring form conjugated molecule, conductivity, photoelectric properties and the non-linear optical property of platinum complex have been strengthened, the part that contains the quinoline group can effectively reduce intermolecular stacking effect, impel and contain quinolyl cyclic metal complexes-platinum complex higher electroluminescent parameter is arranged, the substituting group that contains the quinolyl cyclic metal complexes by adjusting makes the luminescent properties of its platinum complex present phenomenon from orange light to the ruddiness alternation (J.Phys.Chem.C, 2012 from, 116,7526 – 7533).
To reach by force atomic radius little due to the fluorine atom electronegativity, and fluorochemicals has the character of a lot of uniquenesses, has significant application value in the fields such as medicine, functional materials.Especially introduce CF in compound
3After group, because trifluoromethyl has very strong electronegativity, high stability and lipophilicity, therefore, trifluoromethyl is incorporated into thermostability and the emission wavelength that can improve title complex in cyclic metal complexes-platinum complex.
Hole mobile material is the important component part of organic electroluminescence device, as hole mobile material, not only to have lower ionizing potential to reduce the energy barrier between hole transmission layer and anode, higher second-order transition temperature and film-forming properties preferably also should be arranged simultaneously, increase the stability of device with this, extend device lifetime.The triphenylamine analog derivative is the hole mobile material that is most widely used, and has higher hole mobility, be excellent property hole mobile material (J.Mater.Chem., 2010,20,7472-7484).Designed cyclic metal complexes-the platinum complex of the present invention has higher second-order transition temperature, can be used as hole mobile material or hole transport luminescent material and be used for high temperature resistant electroluminescent device, oxygen sensor with its preparation has simple in structure, the advantages such as cost is low, reliable operation, can be made into the portable oxygen sensor and promotes the use of.
Summary of the invention
The purpose of this invention is to provide a kind of Novel ring metal ligand-platinum complex and preparation method thereof and application.
The technical solution used in the present invention is: a kind of Novel ring metal ligand-platinum complex, formed by aryl boric acid compound and synthetic C^N type ring metal neutral ligand and the common complexing platinum of the methyl ethyl diketone ion of halo azepine aromatic compound, and its structure is as follows:
Described halo azepine aromatic compound is selected from 2-bromopyridine, 2-bromo-5-nitropyridine, 2-bromo-5-picoline, 2-bromo-5-cyanopyridine, 2-bromo-5-fluorine pyridine, 2-bromo-6-picoline, 2-bromo-4-picoline, 2-bromo-5-5-flumethiazine, 2-bromoquinoline or 2-chloropyrazine.
Described aryl boric acid compound is selected from phenylo boric acid, 4-methylphenylboronic acid, 4-methoxyphenylboronic acid, 4-trifluoromethyl phenylo boric acid, 4-cyanophenylboronic acid, 4-fluorobenzoic boric acid, 4-(9-carbazyl) phenylo boric acid, 4-triphenylamine boric acid or 3-(N-phenyl) carbazole boric acid.
The preparation method of described Novel ring metal ligand-platinum complex, concrete synthesis step is as follows:
(1) C^N type cyclic metal complexes is synthetic: in air, add successively aryl boric acid 0.375mmol in round-bottomed flask, salt of wormwood 0.5mmol, palladium 0.005mmol, halo azepine aromatic compound 0.25mmol, then, adding volume ratio is the alcohol-water mixing solutions 4mL of 3:1, carry out the Suzuki cross-coupling reaction 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt 15mL, 3 times with 15ml ethyl acetate extraction reaction product, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure biaryl compound,
(2) title complex is synthetic: add potassium platinochloride 0.2mmol, biaryl compound 0.24mmol and 6mL ethylene glycol monoethyl ether/2mL water mixed solution in two mouthfuls of flasks of round bottom, under nitrogen protection in 100 ℃ of magnetic agitation 12h, suction filtration after reaction finishes, use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product; Add dichloro bridge intermediate product, sodium carbonate 1.0mmol, methyl ethyl diketone 2.0mmol and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; under nitrogen protection in 100 ℃ of magnetic agitation 13h; reaction finishes final vacuum and revolves steaming; through column chromatography for separation, obtain analytically pure cyclic metal complexes-platinum complex.
The application of described Novel ring metal ligand-platinum complex is as the material of hole mobile material and making oxygen sensor.
Above-claimed cpd comprises following any derivative:
Compound 1: halo azepine aromatic compound is selected from 2-bromo-5-nitropyridine, and aryl boric acid is selected from 4-triphenylamine boric acid.
Compound 2: halo azepine aromatic compound is selected from 2-bromo-5-picoline, and aryl boric acid is selected from 4-triphenylamine boric acid.
Compound 3: halo azepine aromatic compound is selected from 2-bromo-5-cyanopyridine, and aryl boric acid is selected from 4-triphenylamine boric acid.
Compound 4: halo azepine aromatic compound is selected from the fluorine-based pyridine of 2-bromo-5-, and aryl boric acid is selected from 4-triphenylamine boric acid.
Compound 5: halo azepine aromatic compound is selected from 2-bromo-6-picoline, and aryl boric acid is selected from 4-triphenylamine boric acid.
Compound 6: halo azepine aromatic compound is selected from 2-bromo-4-picoline, and aryl boric acid is selected from 4-triphenylamine boric acid.
Compound 7: halo azepine aromatic compound is selected from 2-bromo-5-5-flumethiazine, and aryl boric acid is selected from 4-triphenylamine boric acid.
Compound 8: halo azepine aromatic compound is selected from the 2-chloropyrazine, and aryl boric acid is selected from 4-triphenylamine boric acid.
Compound 9: halo azepine aromatic compound is selected from 2-bromo-5-5-flumethiazine, and aryl boric acid is selected from phenylo boric acid.
Compound 10: halo azepine aromatic compound is selected from 2-bromo-5-5-flumethiazine, and aryl boric acid is selected from 4-trifluoromethyl phenylo boric acid.
Compound 11: halo azepine aromatic compound is selected from 2-bromo-5-5-flumethiazine, and aryl boric acid is selected from the 4-methoxyphenylboronic acid.
Compound 12: halo azepine aromatic compound is selected from the 2-bromopyridine.Aryl boric acid is selected from 4-trifluoromethyl phenylo boric acid.
Compound 13: halo azepine aromatic compound is selected from 2-bromo-5-5-flumethiazine, and the aryl boric acid compound is selected from the 4-methylphenylboronic acid.
Compound 14: halo azepine aromatic compound is selected from 2-bromo-5-5-flumethiazine, and aryl boric acid is selected from the 4-cyanophenylboronic acid.
Compound 15: halo azepine aromatic compound is selected from 2-bromo-5-5-flumethiazine, and aryl boric acid is selected from the 4-fluorobenzoic boric acid.
Compound 16: halo azepine aromatic compound is selected from the 2-bromoquinoline, and aryl boric acid is selected from the 4-methylphenylboronic acid.
Compound 17: halo azepine aromatic compound is selected from the 2-bromoquinoline, and aryl boric acid is selected from the 4-methoxyphenylboronic acid.
Compound 18: halo azepine aromatic compound is selected from the 2-bromoquinoline, and aryl boric acid is selected from 4-trifluoromethyl phenylo boric acid.
Compound 19: halo azepine aromatic compound is selected from the 2-bromoquinoline, and aryl boric acid is selected from the 4-cyanophenylboronic acid.
Compound 20: halo azepine aromatic compound is selected from the 2-bromoquinoline, and aryl boric acid is selected from the fluorine-based phenylo boric acid of 4-.
Compound 21: halo azepine aromatic compound is selected from the 2-bromoquinoline, and aryl boric acid is selected from the 4-(9-carbazyl) phenylo boric acid.
Compound 22: halo azepine aromatic compound is selected from the 2-bromoquinoline, and aryl boric acid is selected from 4-triphenylamine boric acid.
Compound 23: halo azepine aromatic compound is selected from the 2-bromoquinoline, and aryl boric acid is selected from 3-(N-phenyl) carbazole boric acid.
The invention has the beneficial effects as follows: this Novel ring metal ligand-platinum complex and preparation method thereof and application, this material conveniently is easy to get by the masterplate design, introduce triphenylamine base, quinolyl or trifluoromethyl in material, can regulate easily electronic structure and the hole of material by the substituting group on adjusting azepine aromatic ring and inject and transmission performance.The title complex that the present invention synthesizes has good thermostability and the hole is injected and transmission performance, have a wide range of applications in electroluminescent organic material, oxygen sensing material, dyestuff and medicine and other fields, oxygen sensor with its preparation has simple in structure, the advantages such as cost is low, reliable operation, can be made into the portable oxygen sensor and promotes the use of.
Description of drawings
Fig. 1 is the TGA figure of the compounds of this invention 7.T
g=320°C。
Fig. 2 is the ultraviolet-ray visible absorbing figure of the compounds of this invention 7 solution.
Fig. 3 is the photoluminescence figure of the compounds of this invention 7 solution.
Embodiment
Above-mentioned technical scheme is that the Suzuki cross-coupling reaction by the halo azepine aromatic compound of palladium catalysis and aryl boric acid prepares C^N type cyclic metal complexes biaryl compound, afterwards biaryl compound and Tetrachloroplatinate nak response is prepared cyclic metal complexes-platinum complex.C^N type cyclic metal complexes biaryl compound is that halo azepine aromatic compound, aryl boric acid, salt of wormwood, palladium are joined in the alcohol-water mixing solutions that the 4mL volume ratio is 3:1 for 0.25:0.375:0.5:0.005 in molar ratio, reacted 60～120 minutes in 80 ℃ in air, reaction adds saturated aqueous common salt after finishing, use the ethyl acetate extraction reaction product, merge organic phase, filtrate is concentrated, through column chromatography for separation, obtains analytically pure biaryl compound.Afterwards potassium platinochloride, biaryl compound are joined in 6mL/2mL ethylene glycol monoethyl ether/water mixed solution for 0.20:0.24 in molar ratio; react 12h in 100 ℃ under nitrogen protection; suction filtration after reaction finishes is used respectively normal hexane, washing with alcohol filter cake, obtains dichloro bridge intermediate product.Dichloro bridge intermediate product, sodium carbonate, methyl ethyl diketone are joined in the 6mL ethylene glycol monoethyl ether, and under nitrogen protection, in 100 ℃ of reaction 13h, reaction finishes final vacuum and revolves steaming, obtains analytically pure cyclic metal complexes-platinum complex through column chromatography for separation.The present invention is preparation method and the application of novel C ^N type cyclic metal complexes-platinum complex, and this material conveniently is easy to get by the masterplate design, can regulate easily electronic structure and the hole of material by the substituting group on the adjusting aromatic ring and inject and transmission performance.
Synthesizing of embodiment 1 compound 1
(1) part is synthetic: in air, add successively 4-triphenylamine boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-5-nitropyridine (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure N, the aniline of N-phenylbenzene-4-(5-nitropyridine base-2-).
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), N in two mouthfuls of flasks of round bottom; in N-phenylbenzene-4-(5-nitropyridine base-2-) aniline (0.24mmol), 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; under nitrogen protection in 100 ℃ of magnetic agitation 12h; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; under nitrogen protection in 100 ℃ of magnetic agitation 13h; reaction finishes final vacuum and revolves steaming; through column chromatography for separation, obtain analytically pure compound 1.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, separation yield reaches 37.6%.
Synthesizing of embodiment 2 compounds 2
(1) part is synthetic: in air, add successively 4-triphenylamine boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-5-picoline (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure N, the aniline of N-phenylbenzene-4-(5-picolyl-2-).
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), N in two mouthfuls of flasks of round bottom; N-phenylbenzene-4-(5-picolyl-2-) aniline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; under nitrogen protection in 100 ℃ of magnetic agitation 12h; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; under nitrogen protection in 100 ℃ of magnetic agitation 13h; reaction finishes final vacuum and revolves steaming; through column chromatography for separation, obtain analytically pure compound 2.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, separation yield reaches 41.6%.
Synthesizing of embodiment 3 compounds 3
(1) part is synthetic: in air, add successively 4-triphenylamine boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-5-cyanopyridine (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure N, N-phenylbenzene-4-(5-is cyanopyridine-based-2-) aniline.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), N in two mouthfuls of flasks of round bottom; N-phenylbenzene-4-(5-is cyanopyridine-based-2-) aniline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; under nitrogen protection in 100 ℃ of magnetic agitation 12h; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; under nitrogen protection in 100 ℃ of magnetic agitation 13h; reaction finishes final vacuum and revolves steaming; through column chromatography for separation, obtain analytically pure compound 3.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, separation yield reaches 40.6%.
Synthesizing of embodiment 4 compounds 4
(1) part is synthetic: in air, add successively 4-triphenylamine boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), the fluorine-based pyridine of 2-bromo-5-(0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure N, the aniline of the fluorine-based pyridyl of N-phenylbenzene-4-(5--2-).
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), N in two mouthfuls of flasks of round bottom; the fluorine-based pyridyl of N-phenylbenzene-4-(5--2-) aniline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; under nitrogen protection in 100 ℃ of magnetic agitation 12h; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; under nitrogen protection in 100 ℃ of magnetic agitation 13h; reaction finishes final vacuum and revolves steaming; through column chromatography for separation, obtain analytically pure compound 4.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, separation yield reaches 40.6%.
Synthesizing of embodiment 5 compounds 5
(1) part is synthetic: in air, add successively 4-triphenylamine boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-6-picoline (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure N, the aniline of N-phenylbenzene-4-(6-picolyl-2-).
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), N in two mouthfuls of flasks of round bottom; N-phenylbenzene-4-(6-picolyl-2-) aniline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; under nitrogen protection in 100 ℃ of magnetic agitation 12h; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; under nitrogen protection in 100 ℃ of magnetic agitation 13h; reaction finishes final vacuum and revolves steaming; through column chromatography for separation, obtain analytically pure compound 5.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, separation yield reaches 34.8%.
Synthesizing of embodiment 6 compounds 6
(1) part is synthetic: in air, add successively 4-triphenylamine boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-4-picoline (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure N, the aniline of N-phenylbenzene-4-(4-picolyl-2-).
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), N in two mouthfuls of flasks of round bottom; N-phenylbenzene-4-(4-picolyl-2-) aniline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; under nitrogen protection in 100 ℃ of magnetic agitation 12h; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; under nitrogen protection in 100 ℃ of magnetic agitation 13h; reaction finishes final vacuum and revolves steaming; through column chromatography for separation, obtain analytically pure compound 6.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, separation yield reaches 27.8%.
Synthesizing of embodiment 7 compounds 7
(1) part is synthetic: in air, add successively 4-triphenylamine boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-5-5-flumethiazine (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure N, the aniline of N-phenylbenzene-4-(5-5-flumethiazine base-2-).
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), N in two mouthfuls of flasks of round bottom; N-phenylbenzene-4-(5-5-flumethiazine base-2-) aniline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; under nitrogen protection in 100 ℃ of magnetic agitation 12h; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; under nitrogen protection in 100 ℃ of magnetic agitation 13h; reaction finishes final vacuum and revolves steaming; through column chromatography for separation, obtain analytically pure compound 7.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, separation yield reaches 50.3%.
Synthesizing of embodiment 8 compounds 8
(1) part is synthetic: in air, add successively 4-triphenylamine boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-chloropyrazine (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure N, N-phenylbenzene-4-(pyrazinyl-2, 4-) aniline.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), N in two mouthfuls of flasks of round bottom; N-phenylbenzene-4-(pyrazinyl-2-4-) aniline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; under nitrogen protection in 100 ℃ of magnetic agitation 12h; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; under nitrogen protection in 100 ℃ of magnetic agitation 13h; reaction finishes final vacuum and revolves steaming; through column chromatography for separation, obtain analytically pure compound 8.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, separation yield reaches 5.3%.
Synthesizing of embodiment 9 compounds 9
(1) part is synthetic: in air, add successively phenylo boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-5-5-flumethiazine (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-phenyl-5-5-flumethiazine.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-phenyl-5-5-flumethiazine (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution in two mouthfuls of flasks of round bottom; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 9.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 70.4%.
Synthesizing of embodiment 10 compounds 10
(1) part is synthetic: in air, add successively 4-trifluoromethyl phenylo boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-5-5-flumethiazine (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-trifluoromethyl)-the 5-5-flumethiazine.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-trifluoromethyl in two mouthfuls of flasks of round bottom)-5-5-flumethiazine (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 10.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 37.1%.
Synthesizing of embodiment 11 compounds 11
(1) part is synthetic: in air, add successively 4-methoxyphenylboronic acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-5-5-flumethiazine (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-p-methoxy-phenyl)-the 5-5-flumethiazine.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-p-methoxy-phenyl in two mouthfuls of flasks of round bottom)-5-5-flumethiazine (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 11.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 41.2%.
Synthesizing of embodiment 12 compounds 12
(1) part is synthetic: in air, add successively 4-trifluoromethyl phenylo boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromopyridine (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-trifluoromethyl) pyridine.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-trifluoromethyl in two mouthfuls of flasks of round bottom) pyridine (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 12.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 70.4%.
Synthesizing of embodiment 13 compounds 13
(1) part is synthetic: in air, add successively 4-methylphenylboronic acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-5-5-flumethiazine (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-aminomethyl phenyl)-the 5-5-flumethiazine.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-aminomethyl phenyl in two mouthfuls of flasks of round bottom)-5-5-flumethiazine (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 13.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 41.1%.
Synthesizing of embodiment 14 compounds 14
(1) part is synthetic: in air, add successively 4-cyanophenylboronic acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-5-5-flumethiazine (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-cyano-phenyl)-the 5-5-flumethiazine.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-cyano-phenyl in two mouthfuls of flasks of round bottom)-5-5-flumethiazine (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; after reaction finishes, suction filtration is used normal hexane simultaneously; the washing with alcohol filter cake obtains dichloro bridge intermediate product.Add in dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming; through column chromatography for separation, obtain analytically pure compound 14.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 43.6%.
Synthesizing of embodiment 15 compounds 15
(1) part is synthetic: in air, add successively the fluorine-based phenylo boric acid of 4-(0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromo-5-5-flumethiazine (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make the fluorine-based phenyl of analytically pure 2-(4-)-the 5-5-flumethiazine.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), the fluorine-based phenyl of 2-(4-in two mouthfuls of flasks of round bottom)-5-5-flumethiazine (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 15.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 39.4%.
Synthesizing of embodiment 16 compounds 16
(1) part is synthetic: in air, add successively 4-methylphenylboronic acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromoquinoline (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-aminomethyl phenyl) quinoline.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-aminomethyl phenyl in two mouthfuls of flasks of round bottom) quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 16.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 51.8%..
Synthesizing of embodiment 17 compounds 17
(1) part is synthetic: in air, add successively 4-methoxyphenylboronic acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromoquinoline (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-p-methoxy-phenyl) quinoline.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-p-methoxy-phenyl in two mouthfuls of flasks of round bottom) quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 17.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 46.8%.
Synthesizing of embodiment 18 compounds 18
(1) part is synthetic: in air, add successively 4-trifluoromethyl phenylo boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromoquinoline (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-trifluoromethyl) quinoline.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-trifluoromethyl in two mouthfuls of flasks of round bottom) quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 18.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 41.7%.
Synthesizing of embodiment 19 compounds 19
(1) part is synthetic: in air, add successively 4-cyanophenylboronic acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromoquinoline (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-cyano-phenyl) quinoline.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-cyano-phenyl in two mouthfuls of flasks of round bottom) quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 19.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 49.6%.
Synthesizing of embodiment 20 compounds 20
(1) part is synthetic: in air, add successively 4-fluorobenzoic boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromoquinoline (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-fluorophenyl) quinoline.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-fluorophenyl in two mouthfuls of flasks of round bottom) quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 20.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 49.1%.
Synthesizing of embodiment 21 compounds 21
(1) part is synthetic: in air, add successively the 4-(N-carbazyl in round-bottomed flask) phenylo boric acid (0.375mmol), salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromoquinoline (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-(N-carbazyl) phenyl) quinoline.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-(N-carbazyl in two mouthfuls of flasks of round bottom) phenyl) quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; after reaction finishes, suction filtration is used normal hexane, the washing with alcohol intermediate product simultaneously.Add intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 21.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 57.2%.
Synthesizing of embodiment 22 compounds 22
(1) part is synthetic: in air, add successively triphenylamine boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromoquinoline (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, under 80 ℃ of temperature of reaction, magnetic agitation, carried out the Suzuki cross-coupling reaction 60 minutes, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-(4-(N, N-phenylbenzene amido) phenyl) quinoline.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-(4-(N in two mouthfuls of flasks of round bottom; N-phenylbenzene amido) phenyl) quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 22.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 38.7%.
Synthesizing of embodiment 23 compounds 23
(1) part is synthetic: in air, add successively 3-(N-phenyl) carbazyl boric acid (0.375mmol) in round-bottomed flask, salt of wormwood (0.5mmol), palladium (0.005mmol), 2-bromoquinoline (0.25mmol), then, adding volume ratio is the alcohol-water mixing solutions (4mL) of 3:1, carried out the Suzuki cross-coupling reaction 60 minutes 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt (15mL), with ethyl acetate (3 * 15ml) extractive reaction products, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure 2-((3-(N-phenyl) carbazyl) phenyl) quinoline.
(2) title complex is synthetic: add potassium platinochloride (0.2mmol), 2-((3-(N-phenyl) carbazyl) phenyl) quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution in two mouthfuls of flasks of round bottom; the lower 100 ℃ of magnetic agitation 12h of nitrogen protection; suction filtration after reaction finishes; use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product.Add dichloro bridge intermediate product, sodium carbonate (1.0mmol), methyl ethyl diketone (2.0mmol) and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; the lower 100 ℃ of magnetic agitation 13h of nitrogen protection; reaction finishes final vacuum and revolves steaming, through column chromatography for separation, obtains analytically pure compound 23.Product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 21.7%.
Claims (5)
1. Novel ring metal ligand-platinum complex is characterized in that: formed by aryl boric acid compound and synthetic C^N type ring metal neutral ligand and the common complexing platinum of the methyl ethyl diketone ion of halo azepine aromatic compound, its structure is as follows:
2. Novel ring metal ligand-platinum complex according to claim 1, it is characterized in that: described halo azepine aromatic compound is selected from 2-bromopyridine, 2-bromo-5-nitropyridine, 2-bromo-5-picoline, 2-bromo-5-cyanopyridine, 2-bromo-5-fluorine pyridine, 2-bromo-6-picoline, 2-bromo-4-picoline, 2-bromo-5-5-flumethiazine, 2-bromoquinoline or 2-chloropyrazine.
3. Novel ring metal ligand-platinum complex according to claim 1, it is characterized in that: described aryl boric acid compound is selected from phenylo boric acid, 4-methylphenylboronic acid, 4-methoxyphenylboronic acid, 4-trifluoromethyl phenylo boric acid, 4-cyanophenylboronic acid, 4-fluorobenzoic boric acid, 4-(9-carbazyl) phenylo boric acid, 4-triphenylamine boric acid or 3-(N-phenyl) carbazole boric acid.
4. the preparation method of Novel ring metal ligand-platinum complex according to claim 1, it is characterized in that: the concrete synthesis step of described platinum complex is as follows:
(1) C^N type cyclic metal complexes is synthetic: in air, add successively aryl boric acid 0.375mmol in round-bottomed flask, salt of wormwood 0.5mmol, palladium 0.005mmol, halo azepine aromatic compound 0.25mmol, then, adding volume ratio is the alcohol-water mixing solutions 4mL of 3:1, carry out the Suzuki cross-coupling reaction 80 ℃ of magnetic agitation, follow the tracks of reaction process by tlc, after reacting completely, add saturated aqueous common salt 15mL, 3 times with 15ml ethyl acetate extraction reaction product, merge organic phase, filtrate is concentrated, through column chromatography for separation, make analytically pure biaryl compound,
(2) title complex is synthetic: add potassium platinochloride 0.2mmol, biaryl compound 0.24mmol and 6mL ethylene glycol monoethyl ether/2mL water mixed solution in two mouthfuls of flasks of round bottom, under nitrogen protection in 100 ℃ of magnetic agitation 12h, suction filtration after reaction finishes, use respectively normal hexane, washing with alcohol filter cake, obtain dichloro bridge intermediate product; Add dichloro bridge intermediate product, sodium carbonate 1.0mmol, methyl ethyl diketone 2.0mmol and the 6mL ethylene glycol monoethyl ether that obtains in single necked round bottom flask; under nitrogen protection in 100 ℃ of magnetic agitation 13h; reaction finishes final vacuum and revolves steaming; through column chromatography for separation, obtain analytically pure cyclic metal complexes-platinum complex.
5. the application of Novel ring metal ligand-platinum complex according to claim 1 is characterized in that: described platinum complex is as the material of hole mobile material and making oxygen sensor.
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| CN111875641A (en) * | 2020-08-11 | 2020-11-03 | 大连理工大学 | Preparation method and application of trifluoromethyl modified platinum complex |
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| CN103145763B (en) | 2016-06-15 |
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