CN103059065B - Azo metal complex and preparation method thereof - Google Patents
Azo metal complex and preparation method thereof Download PDFInfo
- Publication number
- CN103059065B CN103059065B CN201110321164.0A CN201110321164A CN103059065B CN 103059065 B CN103059065 B CN 103059065B CN 201110321164 A CN201110321164 A CN 201110321164A CN 103059065 B CN103059065 B CN 103059065B
- Authority
- CN
- China
- Prior art keywords
- metal complex
- indoles
- azo metal
- synthesis
- benzyl
- 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.)
- Expired - Fee Related
Links
Landscapes
- Optical Record Carriers And Manufacture Thereof (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
The invention provides an azo metal complex and a method for synthesis of the azo metal complex. The azo metal complex has a chemical structural formula shown as the following. The compound has the advantages of simple synthesis and high stable performance, and can be used as a blue-ray optical storage material. The metal complex provided in the invention has a structure different from that in the prior art and is used for optical recording materials, and can make use of laser with an ultraviolet absorption wavelength of about 405nm to record information.
Description
Technical field
The invention belongs to light functional dye technical field, be specifically related to a kind of Azo metal complex and preparation method thereof.
Background technology
Now, the various optical record medium such as CD-R/RW, DVD-R/RW is owing to can store jumbo information, be easy to random access, therefore be widely known by the people as the external memory in the signal conditioning package of computer etc., wherein, from the angle of low cost and easily manufacture, the organic pigment system optical recording medium of the recording layer containing organic dye compound being representative with CD-R and DVD-R has advantage.
The situation of the present optical record medium of suitability for industrialized production, it is record, the reading that the laser of about 780nm carries out information that CD-R is designed to be suitable for wavelength, the laser that DVD-R is designed to be suitable for wavelength about 600-700nm carries out record, the reading of information, and it is record, the reading that the laser of about 405nm carries out information that BD-R commercially available is in recent years designed to be suitable for wavelength.
Along with the increase of used quantity of information, people expect the recording density improving medium, and people are just advocating a kind of optical record medium that can record reading information with blue laser to high-density of exploitation in recent years.
Like this, the optical record medium that can read with the record that the laser of longer wavelength carries out information adopted in the past just needs to improve.According to bibliographical information in recent years, the azo-metal chelate containing aromatic heterocycle to be diazo component and β-diketone be coupler component synthesis has absorption in the region of blue light of 350-530nm, and can carry out information record with the laser of 350-530nm.On this basis, being vital to the selection of the diazo component in azo-metal chelate, coupler component and metallo-chelate, is not just can obtain the effective inner complex that can be used for optical storage by simple functional group or selection.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Azo metal complex, can be used for optical recording material, and Useful UV absorbing wavelength carries out the record of information at the laser of about 405nm.
In order to solve the problems of the technologies described above, the invention provides a kind of Azo metal complex, the chemical structural formula of described Azo metal complex is as follows:
The present invention also provides the method for above-mentioned Azo metal complex, adopt following steps: the synthesis of (1) 7-nitro-1H-indoles: 1H-indoles is dissolved in the vitriol oil, be cooled to 0-5 DEG C, the mixed liquid of slow dropping concentrated nitric acid and the vitriol oil, dropwise, react 10-60 minute at continuing 0-5 DEG C, reaction solution is poured in trash ice, be neutralized to PH=6 with strong aqua, obtain 7-nitro-1H-indoles with extraction into ethyl acetate; (2) synthesis of 1-benzyl-7-nitroindoline: be dissolved in DMF by above-mentioned 7-nitro-1H-indoles, be heated to 30-50 DEG C, slowly drips the DMF solution of benzyl chlorine, adds solid sodium carbonate in batches, be then heated to 70-90 DEG C after dropwising, reaction 8-24h.Add water, toluene extraction obtains 1-benzyl-7-nitroindoline; (3) synthesis of 1-benzyl-7-amino indole: above-mentioned 1-benzyl-7-nitroindoline is dissolved in methyl alcohol, adds palladium charcoal, pass into hydrogen, be heated to 50-60 DEG C, when no longer reducing to hydrogen pressure, termination reaction obtains 1-benzyl-7-amino indole; (4) synthesis of benzothiazole diazo liquid: be dissolved in Glacial acetic acid by 2-aminobenzothiazole, be cooled to 0-5 DEG C, drips the vitriol oil, then slowly adds nitrosyl sulfuric acid, dropwises and continues 0-5 DEG C of stirring 20 minutes, obtain benzothiazole diazo liquid; (5) synthesis of coupling product: above-mentioned 1-benzyl-7-amino indole is dissolved in methyl alcohol, drips above-mentioned benzothiazole diazo liquid at 0-5 DEG C, dropwise after stirring is spent the night and obtain coupling product; (6) synthesis of metal complex: add in methyl alcohol by above-mentioned coupling product, adds the methanol solution of cobaltous acetate, filters and obtain described Azo metal complex after reflux 4-8h.
A kind of blue ray optical storage material, comprises above-mentioned Azo metal complex.
The application of described Azo metal complex in light functional dye.
Application in the light functional dye of described Azo metal complex in BDR video disc recording technical field.
Application in the light functional dye of described Azo metal complex in BDR video disc recording technical field, is characterized in that, carries out the record of information with uv-absorbing wavelength at the laser of about 405nm.
The Azo metal complex that the present invention obtains has the advantage that synthesis is simple, stability is high, separately for blue ray optical storage material, also can use with the blue ray optical storage material-mix of other kinds.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of Azo metal complex of the present invention;
Fig. 2 is that Azo metal complex of the present invention absorbs collection of illustrative plates in C3-Fluoroalcohol medium ultraviolet;
Fig. 3 is the thermogravimetric analysis collection of illustrative plates of Azo metal complex of the present invention;
Embodiment
Provide preferred embodiment of the present invention below, and be described in detail, enablely understand function of the present invention, feature better.
According to a particular embodiment of the invention, the preparation of Azo metal complex of the present invention, as shown in Figure 1, adopts following steps:
(1) synthesis of 7-nitro-1H-indoles
0.1mol 1H-indoles (compound 1-1) is dissolved in the 100ml vitriol oil, is cooled to 0-5 DEG C, slowly drips the mixed liquid of 0.11mol concentrated nitric acid and the 22ml vitriol oil, dropwise, react half an hour at continuing 0-5 DEG C, reaction solution is poured in 300g trash ice, be neutralized to PH=6 with strong aqua, with 150ml extraction into ethyl acetate, boil off solvent, obtain dark oil thing, with sherwood oil: ethyl acetate=20: 1 crosses column separating purification, obtain product 10.5g, productive rate: 65%.
(2) synthesis of 1-benzyl-7-nitroindoline:
0.1mol 7-nitroindoline (compound 1-2) is dissolved in 50ml DMF, is heated to 40 DEG C, slowly drips the 30ml DMF solution of 0.12mol benzyl chlorine, adds 0.2mol solid sodium carbonate in batches, be then heated to 80 DEG C after dropwising, reaction 12h.Add 400ml water, 200ml toluene extracts, organic phase anhydrous magnesium sulfate drying.Boil off toluene, obtain 20.2g product, productive rate: 85%.
(3) synthesis of 1-benzyl-7-amino indole:
0.1mol 1-benzyl-7-nitroindoline (compound 1-3) is dissolved in 200ml methyl alcohol, stirring and dissolving, 0.2g palladium charcoal adds, and hydrogen exchange, passes into hydrogen, be heated to 50 to 60 DEG C, termination reaction when no longer reducing to hydrogen pressure, removing palladium charcoal, boils off solvent, obtain product 19.3g, productive rate: 93%.
(4) synthesis of benzothiazole diazo liquid
0.10mol 2-aminobenzothiazole (compound 2-1) is dissolved in 100ml Glacial acetic acid, is cooled to 0-5 DEG C, drips the 22.1ml vitriol oil, then 0.12mol nitrosyl sulfuric acid is slowly added, dropwise and continue 0-5 DEG C of stirring 20 minutes, obtain diazo solution, stand-by.
(5) synthesis of coupling product
0.1mol 1-benzyl-7-amino indole (compound 1-4) is dissolved in 200ml methyl alcohol, benzothiazole diazonium salt (compound 2-2) solution is dripped at 0-5 DEG C, dropwise stirring to spend the night, add 200ml water, stir half an hour, filter, obtain crude product, evaporate to dryness, with anhydrous methanol recrystallization, obtain coupling product (compound 3): 29.9g, productive rate: 81%.
(6) synthesis of metal complex
0.1mol coupling product adds in 100ml methyl alcohol, adds the methanol solution of 0.06mol cobaltous acetate, filters after adding backflow 6h, and solid washing post-drying, obtains end product (compound 4): 35.7g, yield 90%.
This Azo metal complex stability is high, and heat decomposition temperature is at 275 DEG C.
The ultraviolet absorpting spectrum of this Azo metal complex in C3-Fluoroalcohol as shown in Figure 2.
The thermogravimetric analysis collection of illustrative plates of this Azo metal complex as shown in Figure 3.
Azo compound described above, it is in light functional dye, the application particularly in BD-R video disc recording technical field.
The Azo metal complex that the present invention obtains has the advantage that synthesis is simple, stability is high, separately for blue ray optical storage material, also can use with the blue ray optical storage material-mix of other kinds.
Claims (6)
1. an Azo metal complex, is characterized in that, the chemical structural formula of described Azo metal complex is as follows:
2. prepare the method for Azo metal complex as claimed in claim 1, it is characterized in that, adopt following steps:
(1) synthesis of 7-nitro-1H-indoles:
1H-indoles is dissolved in the vitriol oil, is cooled to 0-5 DEG C, slowly drips the mixed solution of concentrated nitric acid and the vitriol oil, dropwise, react 10-60 minute at continuing 0-5 DEG C, reaction solution is poured in trash ice, be neutralized to PH=6 with strong aqua, obtain 7-nitro-1H-indoles with extraction into ethyl acetate;
(2) synthesis of 1-benzyl-7-nitro-1H-indoles:
Above-mentioned 7-nitro-1H-indoles is dissolved in DMF, is heated to 30-50 DEG C, slowly drip the DMF solution of benzyl chlorine, add solid sodium carbonate after dropwising in batches, be then heated to 70-90 DEG C, reaction 8-24h, add water, toluene extraction obtains 1-benzyl-7-nitro-1H-indoles;
(3) synthesis of 1-benzyl-7-amino-1H-indoles:
Above-mentioned 1-benzyl-7-nitro-1H-indoles is dissolved in methyl alcohol, adds palladium carbon, pass into hydrogen, be heated to 50-60 DEG C, when hydrogen pressure no longer reduces, stop reaction, obtain 1-benzyl-7-amino-1H-indoles;
(4) synthesis of benzothiazole diazo liquid:
2-aminobenzothiazole is dissolved in Glacial acetic acid, is cooled to 0-5 DEG C, drip the vitriol oil, then slowly add nitrosyl sulfuric acid, dropwise and continue 0-5 DEG C of stirring 20 minutes, obtain benzothiazole diazo liquid;
(5) synthesis of coupling product:
Above-mentioned 1-benzyl-7-amino-1H-indoles is dissolved in methyl alcohol, drips above-mentioned benzothiazole diazo liquid at 0-5 DEG C, dropwise after stirring is spent the night and obtain coupling product;
(6) synthesis of metal complex:
Above-mentioned coupling product is added in methyl alcohol, adds the methanol solution of cobaltous acetate, filter after reflux 4-8h and obtain described Azo metal complex.
3. a blue ray optical storage material, is characterized in that, comprises Azo metal complex as claimed in claim 1.
4. the application of Azo metal complex in light functional dye as claimed in claim 1.
5. the application in the light functional dye of Azo metal complex as claimed in claim 1 in BDR video disc recording technical field.
6. the application in the light functional dye of Azo metal complex as claimed in claim 5 in BDR video disc recording technical field, is characterized in that, carry out the record of information with uv-absorbing wavelength at the laser of about 405nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110321164.0A CN103059065B (en) | 2011-10-20 | 2011-10-20 | Azo metal complex and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110321164.0A CN103059065B (en) | 2011-10-20 | 2011-10-20 | Azo metal complex and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103059065A CN103059065A (en) | 2013-04-24 |
| CN103059065B true CN103059065B (en) | 2015-04-22 |
Family
ID=48101993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110321164.0A Expired - Fee Related CN103059065B (en) | 2011-10-20 | 2011-10-20 | Azo metal complex and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103059065B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759477A (en) * | 2017-11-20 | 2018-03-06 | 阿里化学(常州)有限公司 | A kind of preparation method of p-nitrophenyl ethylamine hydrochloride |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020127366A1 (en) * | 2000-09-21 | 2002-09-12 | Josef-Walter Stawitz | Optical data stores containing a Co-phthalocyanine complex in the information layer recordable using light |
| CN1745148A (en) * | 2002-11-15 | 2006-03-08 | 兰克赛斯德国有限公司 | Optical data memories comprising cobalt phtalocyanin with an axial substituent and axial ligand in an information photoinscribtible layer |
| CN101237995A (en) * | 2005-08-10 | 2008-08-06 | 三菱化学媒体股份有限公司 | Optical recording medium, azo-type iron chelate coloring matter, and azo-type metal chelate coloring matter additive |
| CN101235213A (en) * | 2007-02-02 | 2008-08-06 | 上海拓引数码技术有限公司 | Light functional dye azo composite and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4351381B2 (en) * | 2000-11-22 | 2009-10-28 | 株式会社リコー | Optical recording medium |
| JP4481000B2 (en) * | 2003-12-25 | 2010-06-16 | 三菱化学メディア株式会社 | Azo metal chelate dye and optical recording medium |
-
2011
- 2011-10-20 CN CN201110321164.0A patent/CN103059065B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020127366A1 (en) * | 2000-09-21 | 2002-09-12 | Josef-Walter Stawitz | Optical data stores containing a Co-phthalocyanine complex in the information layer recordable using light |
| CN1745148A (en) * | 2002-11-15 | 2006-03-08 | 兰克赛斯德国有限公司 | Optical data memories comprising cobalt phtalocyanin with an axial substituent and axial ligand in an information photoinscribtible layer |
| CN101237995A (en) * | 2005-08-10 | 2008-08-06 | 三菱化学媒体股份有限公司 | Optical recording medium, azo-type iron chelate coloring matter, and azo-type metal chelate coloring matter additive |
| CN101235213A (en) * | 2007-02-02 | 2008-08-06 | 上海拓引数码技术有限公司 | Light functional dye azo composite and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103059065A (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4702731B2 (en) | Cyanine dye | |
| JP5320411B2 (en) | Styryl dye | |
| US20050240019A1 (en) | Styryl dyes | |
| CN103059065B (en) | Azo metal complex and preparation method thereof | |
| CN103059598B (en) | Azo blue-ray optical storage dye and preparation method thereof | |
| JP4666869B2 (en) | Cyanine dye | |
| JP4821031B2 (en) | Cyanine dye | |
| CN101235213B (en) | Light functional dye azo composite and preparation method thereof | |
| CN1978443A (en) | Photochromic thiophene pyrazole heterocyclic mixed linkage type asymmetrical dithienylethene compounds, and their preparing method and use | |
| CN102351851B (en) | 4-(5-dimethylaminothiophenevinyl)methylpyridine sulfonate, second-order nonlinear optical crystal of 4-(5-dimethylaminothiophenevinyl)methylpyridine sulfonate, and their preparation methods | |
| CN111004146A (en) | Liquid azophenyl molecular solar thermal fuel and synthesis method and application thereof | |
| CN101602743A (en) | The asymmetric perfluoro-cyclopentene compound of photochromic thiazole hexatomic ring series-parallel type and preparation method and application | |
| CN101712809A (en) | Organic dyestuff and preparation method thereof and recordable optical information recording medium containing organic dyestuff | |
| US5447823A (en) | Metal chelate compound and optical recording medium using the compound | |
| JP4754698B2 (en) | Cyanine dye | |
| CN101250330B (en) | Optical recording dye capable of being used for DVD-R and method for preparing recording layer | |
| CN105001664B (en) | D-pi-A-type aminoazobenzene dye and preparation method therefor | |
| CN101250331B (en) | Optical recording dye capable of being used for DVD-R and method for preparing recording layer | |
| JP2001323179A (en) | Cyanine coloring matter | |
| JP2007090768A (en) | Coloring matter for forming recording layer of optical recording medium, and optical recording medium using it | |
| CN100334158C (en) | High-solubility metal-complex azo dye for DVD-R optical disk | |
| CN101029180B (en) | Azo-dye as light storage medium and its synthesis | |
| US20070218408A1 (en) | Antipyrine Based Azo Metal Complex Dyes and Their Use in Optical Layers for Optical Data Recording | |
| CN101712647A (en) | Metal complex for optical recording material and preparation method as well as prepared optical recording dye thereof | |
| JP4243725B2 (en) | Optical recording medium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150422 Termination date: 20151020 |
|
| EXPY | Termination of patent right or utility model |