CN105669764A - Ruthenium complex containing bisphenol hydroxyl azo naphthol structure and synthesis method and application thereof - Google Patents
Ruthenium complex containing bisphenol hydroxyl azo naphthol structure and synthesis method and application thereof Download PDFInfo
- Publication number
- CN105669764A CN105669764A CN201610004998.1A CN201610004998A CN105669764A CN 105669764 A CN105669764 A CN 105669764A CN 201610004998 A CN201610004998 A CN 201610004998A CN 105669764 A CN105669764 A CN 105669764A
- Authority
- CN
- China
- Prior art keywords
- dipyridyl
- azo
- ruthenium
- filtrate
- containing bisphenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 22
- 239000012327 Ruthenium complex Substances 0.000 title abstract description 4
- 238000001308 synthesis method Methods 0.000 title abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 25
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 21
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 19
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000003086 colorant Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000010189 synthetic method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 2,2 '-dipyridyl-N-oxide compound Chemical class 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229920005654 Sephadex Polymers 0.000 claims description 3
- 239000012507 Sephadex™ Substances 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000011097 chromatography purification Methods 0.000 claims description 3
- 230000003292 diminished effect Effects 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 10
- BZSVVCFHMVMYCR-UHFFFAOYSA-N 2-pyridin-2-ylpyridine;ruthenium Chemical compound [Ru].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 BZSVVCFHMVMYCR-UHFFFAOYSA-N 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 230000008033 biological extinction Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- 229910017673 NH4PF6 Inorganic materials 0.000 abstract 1
- 239000000987 azo dye Substances 0.000 abstract 1
- 238000011085 pressure filtration Methods 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention relates to a ruthenium complex containing a bisphenol hydroxyl azo naphthol structure and a synthesis method and an application thereof. According to the technical schemes, the ruthenium complex containing the bisphenol hydroxyl azo naphthol structure has the structure represented by the formula (I), and the synthesis method includes the steps: mixing [(2,2'-bipyridine)-4-azo]-2,3-dihydroxy naphthalene, cis-[Ru(bpy)2]Cl2.2H2O and anhydrous ethanol, carrying out a reflux reaction for 2-3 h, removing the solvent anhydrous ethanol, adding methanol to a residue, dissolving, carrying out reduced pressure filtration, adding NH4PF6 into the filtrate, to obtain a crude product, and purifying. The complex has the advantages of both azo dyes and ruthenium dyes, has wider absorption range and higher molar extinction coefficient in a visible light region compared with tris(bipyridine) ruthenium, and has a good application prospect in the fields of photoelectric conversion materials and photocatalysis when used as a photosensitive dye.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly relate to a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component and the application as light-sensitive coloring agent thereof.
Background technology
Terpyridyl ruthenium complexe has the advantages such as excellent photoelectrochemistry character, lifetime of excited state length, good stability, is the most frequently used class light-sensitive coloring agent of current photocatalysis field. Its maximum absorption wavelength in visible region is 450nm, and molar extinction coefficient is 1.4 × 104L·mol-1·cm-1, absorption region is 400~550nm. In recent years, in order to obtain the more excellent light-sensitive coloring agent of performance, majority introduces different groups in the structure of tris (bipyridine) ruthenium, by the optimization to its structure, thus expands its absorption region further and improves its molar extinction coefficient. This is also the problem that this area is constantly researched and developed.
Summary of the invention
It is an object of the invention to be incorporated into azo structure in the light-sensitive coloring agent tris (bipyridine) ruthenium structure of excellent performance, synthesize a kind of ruthenium complexe ([Ru (bpy) containing bisphenol hydroxy azo naphthol component2L](PF6)2), this title complex has azoic dyestuff and the advantage of ruthenium dyestuff concurrently, there is wider absorption region compared with tris (bipyridine) ruthenium, higher molar extinction coefficient in visible region, have good application prospect as a kind of light-sensitive coloring agent in photoelectric conversion material, photocatalysis field.
For achieving the above object, the technical solution used in the present invention is: a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component, and its structural formula is as shown in (I):
The synthetic method of above-mentioned a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component, comprises the steps: [(2,2'-dipyridyl)-4-azo-group]-2,3-dihydroxy naphthlene, cis-[Ru (bpy)2]Cl2·2H2O (two hydrations are along two (2,2-dipyridyl) ruthenous chloride), dehydrated alcohol mix, and after back flow reaction 2-3h, except desolventizing dehydrated alcohol, residuum adds dissolve with methanol, filtration under diminished pressure, adds NH in filtrate4PF6, obtain crude product, purify.
The synthetic method of above-mentioned a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component, described purification is: by crude product concentrated filtrate, through sephadex column Chromatographic purification.
The synthetic method of above-mentioned a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component, the synthesis of described [(2,2'-dipyridyl)-4-azo-group]-2,3-dihydroxy naphthlene comprises the steps:
1) 2,2 '-dipyridyl-N-oxide compound is synthesized: by 2,2 '-dipyridyl, H2O2Mixing with glacial acetic acid, 65-75 DEG C of reaction 6-8h, is cooled to room temperature, adds salt of wormwood and regulates pH for neutral, filters and get filtrate, dichloromethane extraction filtrate, collect organic phase, and except desolventizing, product drying, purifies. Preferably, described purification is: product is through silica gel column chromatography, and eluent is methylene dichloride and methyl alcohol.
2) 4-nitro-2,2 is synthesized '-dipyridyl-N-oxide compound: by 2,2 '-dipyridyl-N-oxide compound, when ice-water bath, drip and add the vitriol oil and nitric acid, 75-85 DEG C of reaction 23-25h, cool to room temperature, pour in mixture of ice and water, regulate pH to be neutral, filter, abandon filtrate, filter cake distilled water wash, dry.
3) 4-amino-2 is synthesized, 2 '-dipyridyl: by 4-nitro-2,2 ' in-dipyridyl-N-oxide compound, palladium carbon and dehydrated alcohol mixing, in 75-85 DEG C, under stirring, dripping the mixed solution adding hydrazine hydrate and dehydrated alcohol, reaction 9-11h, is cooled to room temperature, filter, get filtrate, except desolventizing, vacuum-drying. Preferably, hydrazine hydrate to be added in 1h.
4) compound [(2,2'-dipyridyl)-4-azo-group]-2,3-dihydroxy naphthlene (L) is synthesized: by 4-amino-2,2 '-dipyridyl and hydrochloric acid, stir in ice-water bath, under stirring, drip NaNO2The aqueous solution, stir after 10-15min, then add the NaOH solution of 2,3-dihydroxy naphthlene, the pH regulating reaction solution is 7-9, at temperature 0-5 DEG C, stirs 18-20h, adds dichloromethane extraction, collects organic phase, except desolventizing, dry, purifies. Preferably, described purification is: product is through silica gel column chromatography, and eluent is methylene dichloride and methyl alcohol.
The present invention contains the ruthenium complexe ([Ru (bpy) of bisphenol hydroxy azo naphthol component2L](PF6)2) synthetic route as follows:
1, the synthetic route of [(2,2'-dipyridyl)-4-azo-group]-2,3-dihydroxy naphthlene (L)
2、[Ru(bpy)2L](PF6)2Synthetic route
The invention has the beneficial effects as follows:
1. the present invention, has synthesized a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component, increase effectively the conjugated system of tris (bipyridine) ruthenium complex molecule.
2. the ruthenium complexe containing bisphenol hydroxy azo naphthol component of the present invention's synthesis, increases about 1.3 times relative to the molar extinction coefficient of tris (bipyridine) ruthenium, it is seen that light abstraction width obviously expands.
3. the present invention, reacts raw materials used and solvent is all common common agents, does not produce waste gas, environmentally safe.
4. the present invention, purification step is simple, and product rate is relatively high.
5. the present invention, azo structure is incorporated in the light-sensitive coloring agent tris (bipyridine) ruthenium structure of excellent performance, synthesize a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component, this title complex has azoic dyestuff and the advantage of ruthenium dyestuff concurrently, there is in visible region wider absorption region compared with tris (bipyridine) ruthenium, higher molar extinction coefficient, can be used as a kind of light-sensitive coloring agent has good application prospect in photoelectric conversion material, photocatalysis field.
Accompanying drawing explanation
Fig. 1 is [Ru (bpy)2L](PF6)2Mass spectrum.
Fig. 2 is Ru (bpy)3(PF6)2[Ru (bpy)2L](PF6)2At acetonitrile solution, (concentration is 2.5 × 10-5mol·L-1) in uv-visible absorption spectra figure.
Embodiment
Embodiment contains the ruthenium complexe of bisphenol hydroxy azo naphthol component
(1) preparation method is as follows
1, the synthesis of part [(2,2'-dipyridyl)-4-azo-group]-2,3-dihydroxy naphthlene (L)
1) synthesis of 2,2 '-dipyridyl-N-oxide compound
By 2,2 '-dipyridyl (6.40g, 41mmol), H2O2(6mL) mixing with glacial acetic acid (30mL), 70 DEG C of reaction 8h, are cooled to room temperature, add salt of wormwood and regulate pH for neutral, and adularescent is crystalline, and thing precipitates out.Filtrate is got in filtration, dichloromethane extraction filtrate, collects organic phase, except desolventizing, obtains yellow oily liquid. Being purified further by product silica gel column chromatography, taking methylene dichloride and methyl alcohol as eluent, obtain 2,2 '-dipyridyl-N-oxide compound 5.15g, product rate is 73%.
2) 4-nitro-2,2 ' synthesis of-dipyridyl-N-oxide compound
By 2,2 '-dipyridyl-N-oxide compound (6.00g, 34.5mmol), when ice-water bath, drip and add the vitriol oil (10mL) and nitrosonitric acid (10mL). 80 DEG C of reaction 24h, cool to room temperature, pours in the mixture of 150mL ice and water, regulates pH to be neutral with NaOH (4mol/L), has a large amount of yellow substance to precipitate out. Filter, get filter cake, filter cake distilled water wash, dry, obtain yellow solid 4-nitro-2,2 '-dipyridyl-N-oxide compound 2.65g, product rate is 36%.
3) 4-amino-2,2 ' synthesis of-dipyridyl
By 4-nitro-2,2 '-dipyridyl-N-oxide compound (1g, 4.6mmol), 10% palladium carbon (0.2g) and dehydrated alcohol (100mL) mixing, stir under 80 DEG C of conditions, under stirring, drip the mixed solution of add 85% hydrazine hydrate (2mL) and dehydrated alcohol (20mL), control hydrazine hydrate adds at about 1h, and reaction 10h, is cooled to room temperature, it is filtered to remove palladium carbon, get filtrate, except desolventizing, vacuum-drying, obtaining product is light yellow solid 0.74g, and product rate is 95%.
4) synthesis of part [(2,2'-dipyridyl)-4-azo-group]-2,3-dihydroxy naphthlene (L)
By 4-amino-2,2 '-dipyridyl (258mg, 1.5mmol), hydrochloric acid (5mL, 5mol/L), stirs in ice-water bath, drips NaNO2Aqueous solution 1mL (1.5mmol), stir 10min, then add 2, NaOH (24mmol) the solution 12mL of 3-dihydroxy naphthlene (240mg, 1.5mmol), regulates reaction solution pH7~9, at temperature 0~5 DEG C, stirring reaction 18h, adds dichloromethane extraction, collect organic phase, except desolventizing, dry, product silica gel column chromatography is further purified, taking methylene dichloride and methyl alcohol as eluent, final that product be red solid 178mg, product rate is 35%.
2、[Ru(bpy)2L](PF6)2Synthesis
By [(2,2'-dipyridyl)-4-azo-group]-2,3-dihydroxy naphthlene (68g, 0.2mmol), cis-[Ru (bpy)2]Cl2·2H2O (104mg, 0.2mmol) and the mixing of 20mL dehydrated alcohol, back flow reaction 2h, except desolventizing, after residuum adds dissolve with methanol, filtration under diminished pressure, adds NH in filtrate4PF6, stirring, concentrated filtrate, through sephadex column Chromatographic purification, obtaining total product is atropurpureus solid 117mg, and product rate is 77%.
(2) detected result is as follows
1)[Ru(bpy)2L](PF6)2Elemental Analysis theory (%): C45.94, H2.89, N10.72; Ultimate analysis experimental value (%): C45.52, H2.43, N11.03.
2) title complex [Ru (bpy)2L](PF6)2Mass spectrum as shown in Figure 1, wherein, m/z=377.9 peak is attributed to [M-2PF6]2+The peak of/2 molions, m/z=755.1 peak is attributed to [M-2PF6-H]+The peak of molion.
3)[Ru(bpy)2L](PF6)2Ultraviolet-visible light spectrogram in acetonitrile solution as shown in Fig. 2 and following table, as shown in Figure 2: title complex [Ru (bpy)2L](PF6)2At the absorption region 400~650nm of visible region, λmaxAt 505nm place, with tris (bipyridine) ruthenium (Ru (bpy)3(PF6)2) compare visible region absorption region and obviously widen, molar extinction coefficient increases about 1.3 times.
(3) apply
Azoic dyestuff and ruthenium dye structure are organically combined by the ruthenium dyestuff of the present invention's synthesis, all have very strong absorption at visible region 400-650nm, and good stability, can be used as light-sensitive coloring agent for multiple research field such as dye sensitization solar battery, photochemical catalysis.
Claims (7)
1. one kind contains the ruthenium complexe of bisphenol hydroxy azo naphthol component, it is characterised in that, its structural formula is as shown in (I):
2. the synthetic method of a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component according to claim 1, it is characterized in that, comprise the steps: [(2,2'-dipyridyl)-4-azo-group]-2,3-dihydroxy naphthlene, cis-[Ru (bpy)2]Cl2·2H2O, dehydrated alcohol mix, and after back flow reaction 2-3h, except desolventizing, residuum adds dissolve with methanol, filtration under diminished pressure, adds NH in filtrate4PF6, obtain crude product, purify.
3. the synthetic method of a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component according to claim 2, it is characterised in that, described purification is: by crude product concentrated filtrate, through sephadex column Chromatographic purification.
4. the synthetic method of a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component according to claim 2, it is characterised in that, the synthesis of described [(2,2'-dipyridyl)-4-azo-group]-2,3-dihydroxy naphthlene comprises the steps:
1) 2,2 '-dipyridyl-N-oxide compound is synthesized: by 2,2 '-dipyridyl, H2O2Mixing with glacial acetic acid, 65-75 DEG C of reaction 6-8h, is cooled to room temperature, adds salt of wormwood and regulates pH for neutral, filters and get filtrate, dichloromethane extraction filtrate, collect organic phase, and except desolventizing, product drying, purifies;
2) 4-nitro-2,2 is synthesized '-dipyridyl-N-oxide compound: by 2,2 '-dipyridyl-N-oxide compound, when ice-water bath, drip and add the vitriol oil and nitric acid, 75-85 DEG C of reaction 23-25h, cool to room temperature, pour in mixture of ice and water, regulate pH to be neutral, filter, abandon filtrate, filter cake distilled water wash, dry;
3) 4-amino-2 is synthesized, 2 '-dipyridyl: by 4-nitro-2,2 '-dipyridyl-N-oxide compound, palladium carbon and dehydrated alcohol mixing, in 75-85 DEG C, under stirring, dripping the mixed solution adding hydrazine hydrate and dehydrated alcohol, reaction 9-11h, is cooled to room temperature, filter, get filtrate, except desolventizing, vacuum-drying;
4) compound [(2,2'-dipyridyl)-4-azo-group]-2,3-dihydroxy naphthlene is synthesized: by 4-amino-2,2 '-dipyridyl and hydrochloric acid, stir in ice-water bath, under stirring, drip NaNO2The aqueous solution, stir after 10-15min, then add the NaOH solution of 2,3-dihydroxy naphthlene, the pH regulating reaction solution is 7-9, at temperature 0-5 DEG C, stirs 18-20h, adds dichloromethane extraction, collects organic phase, except desolventizing, dry, purifies.
5. the synthetic method of a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component according to claim 4, it is characterized in that, step 1) and step 4) described in purification be: product is through silica gel column chromatography, and eluent is methylene dichloride and methyl alcohol.
6. the synthetic method of a kind of ruthenium complexe containing bisphenol hydroxy azo naphthol component according to claim 4, it is characterised in that, step 3) in, hydrazine hydrate adds in 1h.
7. the ruthenium complexe containing bisphenol hydroxy azo naphthol component according to claim 1 is in the application prepared in light-sensitive coloring agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610004998.1A CN105669764A (en) | 2016-01-04 | 2016-01-04 | Ruthenium complex containing bisphenol hydroxyl azo naphthol structure and synthesis method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610004998.1A CN105669764A (en) | 2016-01-04 | 2016-01-04 | Ruthenium complex containing bisphenol hydroxyl azo naphthol structure and synthesis method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105669764A true CN105669764A (en) | 2016-06-15 |
Family
ID=56298950
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610004998.1A Pending CN105669764A (en) | 2016-01-04 | 2016-01-04 | Ruthenium complex containing bisphenol hydroxyl azo naphthol structure and synthesis method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105669764A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108276305A (en) * | 2018-01-06 | 2018-07-13 | 江西理工大学 | A method of mild prepares Sudan red 1 analogue |
CN115197127A (en) * | 2022-06-14 | 2022-10-18 | 广州大学 | Ruthenium-containing complex, preparation method and application thereof |
-
2016
- 2016-01-04 CN CN201610004998.1A patent/CN105669764A/en active Pending
Non-Patent Citations (1)
Title |
---|
王立飞: "含偶氮萘酚结构的2,2’-联吡啶衍生物及其多吡啶钌配合物的合成与表征", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108276305A (en) * | 2018-01-06 | 2018-07-13 | 江西理工大学 | A method of mild prepares Sudan red 1 analogue |
CN108276305B (en) * | 2018-01-06 | 2020-07-31 | 江西理工大学 | Mild method for preparing Sudan red I structural analogue |
CN115197127A (en) * | 2022-06-14 | 2022-10-18 | 广州大学 | Ruthenium-containing complex, preparation method and application thereof |
CN115197127B (en) * | 2022-06-14 | 2023-09-29 | 广州大学 | Ruthenium-containing complex, preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Sun et al. | Enhancement of visible-light-driven CO 2 reduction performance using an amine-functionalized zirconium metal–organic framework | |
CN101704824B (en) | Catalytic preparation method of dicyclopentadiene dioxide by quaternary ammonium heteropoly phosphato tungstate | |
CN103772297A (en) | Chiral hexahydroxy n-heterocyclic carbine precursor compound as well as preparation method and application thereof | |
CN105669764A (en) | Ruthenium complex containing bisphenol hydroxyl azo naphthol structure and synthesis method and application thereof | |
CN103408962A (en) | Organic dye containing benzothiadiazole-thienocyclopenta and applications of organic dye in dye-sensitized solar cells | |
CN108863840A (en) | The fluorinated derivatives and preparation method thereof of azo-based benzene | |
CN104073018A (en) | A series of 2,3,5,6-quaterthiophene substituted BODIPY (boron dipyrromethene) dyes with long wave absorption characteristics and preparation method of 2,3,5,6-quaterthiophene substituted BODIPY dyes | |
CN101463011B (en) | Process for synthesizing 3,4-dihydropyrimidine-2-keto | |
Jia et al. | Luminescent lanthanide-2-phenylpyrimidine-carboxylate frameworks: structure and luminescence tuning | |
CN101941971B (en) | Method for synthesizing evodiamine | |
CN108997591B (en) | Visible-light response hafnium-based metal organic framework material and preparation method thereof | |
CN109422700A (en) | A kind of synthetic method of N- acetyl group quinoxaline -2- amide and its derivative | |
CN108863841A (en) | A kind of ortho position fluoro azobenzene derivatives and preparation method thereof | |
CN105294540A (en) | Novel Schiff base compound taking triphenylamine as center and preparation of novel Schiff base compound | |
CN110590853B (en) | Urea group-containing platinum pyridyl complex with anion recognition function and preparation method thereof | |
CN107382819A (en) | A kind of preparation method of 3 thioindole class compound | |
CN103172677A (en) | Organic metal iridium complex luminescent material and synthetic method of material | |
CN103145559A (en) | Preparation method of N-allyl arylamine | |
CN108586540B (en) | Ruthenium (II) bisoxazoline pyridine compound, preparation method thereof and catalytic reduction method of aromatic nitro compound | |
CN105348285A (en) | Low-cost and high-yield adenine preparation method | |
CN104211652A (en) | Method for preparing plerixafor | |
CN109912661A (en) | Pyrimidine with catalytic performance-pyrazoles ruthenium complex and preparation method thereof | |
CN103193784B (en) | A kind of containing pyrimidine group rigidity Conjugate macrocycle compound and its preparation method and application | |
CN104402930B (en) | A kind of symmetry benzimidazole ruthenium complex and preparation method thereof | |
CN113024506B (en) | Process for preparing 3-formyltetrahydrothiopyran compounds |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160615 |