CN100484926C - Chelate of azo metals, and preparation method - Google Patents
Chelate of azo metals, and preparation method Download PDFInfo
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Abstract
This invention discloses a method for preparing metal-azo chelate compound as the recording medium in 635-650 nm recordable disks with super-resolution near field structure. The metal-azo chelate compound is 2-(5-ethylthio-1, 3, 4-thiadiazole-azo)-5-(N, N-diethyl) trifluoromethyl benzenesulfonamide chelated Ni, Co, Cu, Zn or Mn. The structure is shown in formula I, where, C and N are carbon and nitrogen; S and F are sulfur and fluorine; R is H or C1-C4 alkyl; M2+ is Ni2+, Co2+, Cu2+, Zn2+ or Mn2+.. The metal-azo chelate compound is easy to synthesize, and has such advantages as high yield, high light and thermal stability, and high solubility in organic solvents. The metal-azo chelate compound can be prepared into films by spin coating. The maximal absorption wavelength of the film is 610-630 nm. The film can be used as the recording medium in red-light recordable disks with super-resolution near field structure.
Description
Technical field
The present invention relates to the synthetic method of azoic dyestuff and metallo-chelate thereof, particularly a kind of wavelength that is used for is azo-metal chelate of the recording materials of 635-650nm with compact disc recordable of ultra-resolution near-field structure and preparation method thereof.
Background technology
Information technology is the gordian technique of 21 century, and in the obtaining, transmit, store, show, handle of information, information storage is one of crucial.Disk, semi-conductor random memory and optical storage are present three kinds of main data storage methods.The information carrier of optical storage is a photon, it can enter into electron carrier inaccessiable high-density, vast capacity, ultrafast speed and parallel I/O and highly interconnected field.In the CD storage technique, the modulating lasering beam of carrying information belongs to the far field optical recording by object lens focusing record on the optical disk medium layer at present, and the size of measuring point is decided by the diffraction limit of focused light.And the focal beam spot diameter is relevant with recording laser wavelength and numerical aperture, and being formulated is exactly D=0.56 λ/NA, and storage density is proportional to (NA/ λ)
2, the numerical aperture that therefore shortens recording laser wavelength and raising object lens is to improve two kinds of effective ways of optical storage density.It is the DVD series of main flow with single face capacity 4.7GB that present optical disc product has developed into the s-generation.Red light semiconductor laser (630-650nm) and numerical aperture are 0.6 object lens.Compare storage capacity with the CD CD and improved 7-8 doubly.The Blu-ray Disc (the recording laser wavelength is 400-500nm) of super-high density also goes on the market now, and the single face capacity is about 22.5Gb.In several years of future, by shortening the numerical aperture of recording laser wavelength and raising object lens, storage density on optical discs also can improve, but the raising of this density only is several times a relation, and the increase of numerical aperture be with the minimizing of depth of focus and since the distortion that excentricity causes add cost greatly, it is also very limited to improve storage density with this.
Recently, the optical near-field technology is subjected to increasing attention, use this technology can write down and read the measuring point of 40-80nm size, yet the optical near-field technology also has a lot of problems to overcome, the problem frangible as the near field probe, the problem of the slow response of slit control between probe and the medium, narrow and record of record area and reading speed be problem slowly, and these problems have limited the practice of optical near-field technology in information storage.
Ultra-resolution near-field structure (Super-RENS) (Appl.Phys.Lett.73 (1998) 2078) technology is a kind of new technology that integrates super resolution optical disc technology and near field of light memory technology that development in recent years is got up, this technological breakthrough the restriction of traditional optical storage to diffraction limit.And the distance of near field is to control by the sealing coat between mask layer and the recording layer, and physical disturbance seldom, does not pollute and has very high writing speed, is considered to one of the most effective near-field optical recording.And along with progress of research, ultra-resolution near-field structure has experienced from Sb type (aperture type) AgOx type finally and the PtOx type (oval bubble type) that proposes recently, and signal to noise ratio also moves closer to the requirement of practicability.
But because the restriction of CD intellecture property, the situation of China's CD industry development is very awkward.Propose a kind of multifunctional optical disk of new generation (next-generation versatile disc) recently, be called for short NVD (academic conference in 2006 of Chinese optics association, GuangZhou, China, 2006,374).Its core is to develop the high-definition red-laser optic disk physical format with independent intellectual property right.By adopting the high-density master imprinting technology of autonomous innovation, optical ultra-discrimination technology and ultra-resolution near-field structure (Super-RENS) technology etc. improve the storage capacity of CD greatly.Wherein introduce the Super-RENS technology, can make storage density on optical discs bring up to single-surface double-layer 25GB, this has improved about 16GB than traditional single-surface double-layer DVD, satisfies the requirement of high definition video program storage capacity.
But the more of ultra-resolution near-field structure CD research at present is phase change disc, magnetooptic disc and read-only disc, and used recording materials are inorganic materials, and to a compact disc recordable research of ultra-resolution near-field structure seldom.Although organic materials has been used for a compact disc recordable of ruddiness (DVD-R) (US2003/235783 A1) and Blu-ray Disc, but the structure of a compact disc recordable of ultra-resolution near-field structure is different with the DVD-R compact disk structure, originally is used for the recording medium of DVDR and is not suitable for use in once can recording the recording medium of ultra-resolution near-field structure NVD CD.Someone once studied cyanine dye and was used for compact disc recordable of ultra-resolution near-field structure (Jpn.J.Appl.Phys.Vol.42 (2003) 997), but there is poor heat stability in cyanine dye, be lower than the diffraction limit measuring point to read signal to noise ratio low, also have very big gap from practicability.Therefore need to select a kind of maximum absorption wavelength to meet the demands, the dyestuff that photo and thermal stability is good, this dyestuff has higher heat decomposition temperature, so that satisfying the requirement of compact disc recordable of ultra-resolution near-field structure to the thermostability of recording materials in the readout continuously.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the defective of above-mentioned prior art, for service band provides a kind of azo-metal chelate and preparation method thereof at the ultra-resolution near-field structure video disc recording layer of once can recording of 635-650nm, the maximum absorption of this metal azo inner complex film is between 550-650nm, it is big to have solubleness in C3-Fluoroalcohol, is suitable for spin-coating film; The utilization of medium of can in ruddiness ultra-resolution near-field structure compact disc recordable, noting down, and have effect preferably.And requiring the preparation method to be easy to control, the productive rate height does not have particular requirement to reaction system.
Technical solution of the present invention is as follows:
A kind of metal azo inner complex that once can record ultra-resolution near-field structure video disc recording layer at 635-650nm, the name of this metal azo inner complex is called 2-(5-alkyl sulfenyl-1,3,4-thiadiazolyl group azo)-5-(N, N-diethyl)-the trifluoromethyl sulfonanilide closes Ni, or Co, or Cu, or Zn, or Mn, be characterised in that its structural formula is as follows:
Wherein: C and N represent carbon and nitrogen respectively;
S and F represent sulphur and fluorine respectively
R represents H, C
1-C
4Alkyl;
M
2+Be nickel, or cobalt, or copper, or zinc, or the manganese divalent-metal ion.
The preparation method of described metal azo inner complex is characterized in that comprising the following steps:
1. diazotization reaction:
It is in 85% the phosphoric acid that diazo component is dissolved in an amount of concentration, ice bath is cooled to 0～5 ℃, under agitation with solid sodium nitrite, joined in the above-mentioned solution at 20-40 minute, the mol ratio of described Sodium Nitrite and diazo component is 1.05～1.10:1, stirring reaction 2 hours, if then illustrating, solution turned blue contains excessive nitrous acid, coupled reaction to next step is unfavorable, removes with urea, obtains the transparent diazotization solution of reddish-brown at last;
2. coupled reaction:
Mol ratio in coupling component and diazo component is the ratio weighing 3-(N of 1.1:1, N-diethyl amido) the trifluoromethyl sulfonanilide is made coupling component, coupling component and anhydrous sodium acetate be dissolved in the Erlenmeyer flask that fills anhydrous methanol form methanol solution, wherein: coupling component: anhydrous sodium acetate: the weight ratio of anhydrous methanol is 1:1:20, be cooled to 0～5 ℃ with ice bath, described diazotization solution was added drop-wise in the described methanol solution at 30-60 minute, fully stirring reaction is 3～10 hours, then add deionized water and continue stirring reaction more than 1 hour, after the standing over night, filter, washing, drying obtains azoic dyestuff.
3. chelatropic reaction:
(a) get following raw materials by weight percent
Azoic dyestuff: 3-5wt%
Nickelous acetate (or cobaltous acetate, or zinc acetate, or venus crystals, or manganous acetate): 2-4wt%
Tetrahydrofuran (THF): 50-60wt%
Anhydrous methanol: 30-40wt%
Anhydrous sodium acetate: 3-7wt%
(b) azoic dyestuff is dissolved in forms tetrahydrofuran solution in the tetrahydrofuran (THF), with nickelous acetate (or cobaltous acetate, or zinc acetate, or venus crystals, or manganous acetate) is dissolved in the anhydrous methanol, in 20-60 ℃ of scopes, this methanol solution was joined in the described tetrahydrofuran solution in 20 minutes, reacted 5-10 hours;
(c) back that reacts completely adds water coolant, separates out crystal, and overanxious, washing, drying obtain metal azo inner complex.
Described diazo component is 2-amino-5-methyl sulfenyl-1,3,4-thiadiazoles;
Or 2-amino-5-ethyl sulfenyl-1,3,4-thiadiazoles;
Or 2-amino-5-propyl group sulfenyl-1,3,4-thiadiazoles;
Or 2-amino-5-butyl sulfenyl-1,3,4-thiadiazoles;
Or 2-amino-5-thiohydroxy-1,3,4-thiadiazoles.
Described diazo component and concentration are that the weight ratio of 85% phosphoric acid is 20～30:1.
The mol ratio of described coupling component and diazo component is 1.1:1.
Technique effect of the present invention is as follows:
Azoic dyestuff decomposition temperature height of the present invention, Heat stability is good; The maximum absorption of metal azo inner complex film is between 550-650nm, and solubleness is suitable for spin-coating film greater than 4% in C3-Fluoroalcohol; Described azo-metal chelate, the utilization of medium of can in ruddiness ultra-resolution near-field structure compact disc recordable, noting down, and have effect preferably.The present invention has reaction conditions and is easy to control, and the productive rate height does not have characteristics such as particular requirement to reaction system; Preparation method of the present invention both had been fit to prepared in laboratory, was fit to suitability for industrialized production again.
Description of drawings
Fig. 1 is the azoic dyestuff of the embodiment of the invention 1 preparation and nickel metallo-chelate thereof the absorption spectrum at solution and film, wherein A is the absorption spectrum of azoic dyestuff in chloroform, B is the absorption spectrum of its nickel metallo-chelate in chloroform, and C is dissolved in the absorption spectrum of the film that (20mg/ml) back prepares in the C3-Fluoroalcohol on the K9 sheet glass for its nickel metallo-chelate.
Fig. 2 is the azoic dyestuff of the embodiment of the invention 2 preparation and nickel metallo-chelate thereof the absorption spectrum at solution and film, wherein A is the absorption spectrum of azoic dyestuff in chloroform, B is the absorption spectrum of its nickel metallo-chelate in chloroform, and C is dissolved in the absorption spectrum of the film that (20mg/ml) back prepares in the C3-Fluoroalcohol on the K9 sheet glass for its nickel metallo-chelate.
Embodiment
Further specify the present invention below in conjunction with embodiment and accompanying drawing and utilization example.
Embodiment 1:
Diazotization reaction: take by weighing 2-amino-5-ethyl sulphur-1,3, it is (phosphoric acid and diazo component weight percent are 20:1) in 85% the phosphoric acid that 4-thiadiazoles 0.01mol (1.61g) is dissolved in concentration, is cooled to 0-5 ℃ with ice bath.Under agitation solid sodium nitrite 0.0105mol (0.72g) was joined in the above-mentioned solution in 30 minutes, fully stirring reaction is 2 hours.Whether with starch KI test paper check HNO2 excessive, contain excessive nitrous acid if become blue then explanation if having reacted the back, unfavorable to next step coupled reaction, removes with urea, obtains the transparent diazotization solution of reddish-brown at last.
Coupled reaction: with the coupling component (3-(N of 0.011mol (3.26g), the N-Diethyl Aniline) trifluoromethane sulfonanilide) and anhydrous sodium acetate be dissolved in the Erlenmeyer flask that fills anhydrous methanol coupling component wherein: anhydrous sodium acetate: the weight ratio of anhydrous methanol is 1:1:20).Be cooled to 0-5 ℃ with ice bath, diazotization solution was added drop-wise in 40 minutes in the above-mentioned methanol solution, fully stirring reaction is 4 hours, then adds the 100ml deionized water and continues stirring reaction 1 hour.After the standing over night, filtration, washing, drying obtain the thick azoic dyestuff of 4.02g, and theoretical yield 4.68g, yield are 86.10%.Dyestuff is purified with silica gel column chromatography, and elutriant is a trichloromethane.The dyestuff fusing point is 174-176 ℃.Dye structure is
Fig. 1 is the azoic dyestuff of the embodiment of the invention 1 preparation and nickel metallo-chelate thereof the absorption spectrum at solution and film, wherein A is the absorption spectrum of azoic dyestuff in chloroform, B is the absorption spectrum of its nickel metallo-chelate in chloroform, and C is dissolved in the absorption spectrum of the film that (20mg/ml) back prepares in the C3-Fluoroalcohol on the K9 sheet glass for its nickel metallo-chelate.
Embodiment 2:
Diazotization reaction: take by weighing 2-amino-5-sulfhedryl-1,3, it is that wherein: phosphoric acid and diazo component weight ratio are 25:1, are cooled to 0～5 ℃ with ice bath in 85% the phosphoric acid that 4-thiadiazoles 0.01mol (1.33g) is dissolved in concentration.Under agitation solid sodium nitrite 0.0105mol (0.72g) was joined in 30 minutes in the above-mentioned solution, fully stirring reaction is 2 hours.Whether with starch KI test paper check HNO2 excessive, contain excessive nitrous acid if become blue then explanation if having reacted the back, unfavorable to next step coupled reaction, removes with urea, obtains the transparent diazotization solution of reddish-brown at last.
Coupled reaction: with the coupling component 3-(N of 0.011mol (3.26g), the N-Diethyl Aniline) trifluoromethane sulfonanilide and anhydrous sodium acetate are dissolved in the Erlenmeyer flask that fills anhydrous methanol, wherein: coupling component: anhydrous sodium acetate: the weight ratio of anhydrous methanol is 1:1:20.Be cooled to 0～5 ℃ with ice bath, diazotization solution was added drop-wise in 40 minutes in the above-mentioned methanol solution, fully stirring reaction is 4 hours, then adds the 100ml pure water and continues stirring reaction 1 hour.After the standing over night, filtration, washing, drying obtain the thick azoic dyestuff of 3.03g, and theoretical yield 4.40g, yield are 68.75%.Dyestuff is purified with silica gel column chromatography, and elutriant is a trichloromethane.The dyestuff fusing point is 142～144 ℃.Dye structure is
Fig. 2 is the azoic dyestuff of the embodiment of the invention 2 preparation and nickel metallo-chelate thereof the absorption spectrum at solution and film, wherein A is the absorption spectrum of azoic dyestuff in chloroform, B is the absorption spectrum of its nickel metallo-chelate in chloroform, and C is dissolved in the absorption spectrum of the film that (20mg/ml) back prepares in the C3-Fluoroalcohol on the K9 sheet glass for its nickel metallo-chelate.
Embodiment 3:
Diazotization reaction: take by weighing 2-amino-5-methyl sulfenyl-1,3, it is that wherein: the weight ratio of phosphoric acid and diazo component is 25:1, is cooled to 0～5 ℃ with ice bath in 85% the phosphoric acid that 4-thiadiazoles 0.01mol (1.47g) is dissolved in concentration.Under agitation solid sodium nitrite 0.0105mol (0.72g) was joined in 30 minutes in the above-mentioned solution, fully stirring reaction is 2 hours.Whether with starch KI test paper check HNO2 excessive, contain excessive nitrous acid if become blue then explanation if having reacted the back, unfavorable to next step coupled reaction, removes with urea, obtains the transparent diazotization solution of reddish-brown at last.
Coupled reaction: with the coupling component 3-(N of 0.011mol (3.26g), the N-Diethyl Aniline) trifluoromethane sulfonanilide and anhydrous sodium acetate are dissolved in the Erlenmeyer flask that fills anhydrous methanol, wherein: coupling component: anhydrous sodium acetate: the weight ratio of anhydrous methanol is 1:1:20.Be cooled to 0～5 ℃ with ice bath, diazotization solution was added drop-wise in 40 minutes in the above-mentioned methanol solution, fully stirring reaction is 4 hours, then adds the 100ml pure water and continues stirring reaction 1 hour.After the standing over night, filtration, washing, drying obtain the thick azoic dyestuff of 3.43g, and theoretical yield 4.54g, yield are 75.6%.Dyestuff is purified with silica gel column chromatography, and elutriant is a trichloromethane.The dyestuff fusing point is 152～154 ℃.Dye structure is
Embodiment 4
(a) take by weighing embodiment one synthetic azoic dyestuff in following ratio and carry out the metal-chelating reaction:
Azoic dyestuff: 3wt%
Four water nickelous acetate: 2wt%
Tetrahydrofuran (THF): 55wt%
Anhydrous methanol: 35wt%
Anhydrous sodium acetate: 5wt%
(b) azoic dyestuff is dissolved in the tetrahydrofuran (THF), nickelous acetate is dissolved in the anhydrous methanol, when temperature is 20 ℃, methanol solution was joined in the tetrahydrofuran solution about 60 minutes, reacted 5 hours;
(c) back that reacts completely adds the water coolant of 50ml, separates out crystal, and overanxious, washing, drying obtain metal azo inner complex 2-(5-ethyl sulfenyl-1,3,4-thiadiazolyl group azo)-5-(N, N-diethyl)-trifluoromethyl sulfonanilide and close nickel chelate.
Under same condition, use cobaltous acetate, or zinc acetate, or venus crystals, or metal-salt such as manganous acetate replaces nickelous acetate, can obtain the corresponding cobalt chelates of said structure, chelates of zinc, copper chelate, manganic chelates etc.
Embodiment 5
(a) take by weighing embodiment 2 synthetic azoic dyestuffs in following ratio and carry out the metal-chelating reaction:
Azoic dyestuff: 4wt%
Cobaltous acetate: 2.5wt%
Tetrahydrofuran (THF): 50wt%
Anhydrous methanol: 40wt%
Anhydrous sodium acetate: 3.5wt%
(b) azoic dyestuff is dissolved in the tetrahydrofuran (THF), cobaltous acetate is dissolved in the anhydrous methanol, when temperature is 40 ℃, methanol solution was joined in the tetrahydrofuran solution about 40 minutes, reacted 7.5 hours;
(c) back that reacts completely adds the water coolant of 50ml, separates out crystal, and overanxious, washing, drying obtain metal azo inner complex 2-(5-sulfhedryl-1,3,4-thiadiazolyl group azo)-5-(N, N-diethyl)-trifluoromethyl sulfonanilide and close cobalt chelates.
Under same condition, use nickelous acetate, or zinc acetate, or venus crystals, or metal such as manganous acetate replaces cobaltous acetate, can obtain the corresponding nickel chelate of said structure, chelates of zinc, copper chelate, manganic chelates etc.
Embodiment 6
(a) take by weighing embodiment 3 synthetic azoic dyestuffs in following ratio and carry out the metal-chelating reaction:
Azoic dyestuff: 5wt%
Cobaltous acetate: 4wt%
Tetrahydrofuran (THF): 57wt%
Anhydrous methanol: 30wt%
Anhydrous sodium acetate: 4wt%
(b) azoic dyestuff is dissolved in the tetrahydrofuran (THF), zinc acetate is dissolved in the anhydrous methanol, when temperature is 20 ℃, methanol solution was joined in the tetrahydrofuran solution in 60 minutes, reacted 10 hours;
(c) back that reacts completely adds the water coolant of 50ml, separates out crystal, and overanxious, washing, drying obtain metal azo inner complex 2-(5-methyl sulfenyl-1,3,4-thiadiazolyl group azo)-5-(N, N-diethyl)-trifluoromethyl sulfonanilide and close chelates of zinc.
Under same condition, with nickelous acetate or cobaltous acetate, or venus crystals, or metal-salt such as manganous acetate replaces nickelous acetate, can obtain the corresponding nickel chelate of said structure, cobalt chelates, copper chelate, manganic chelates etc.
Metallo-chelate provided by the invention, its maximum absorption wavelength have bigger absorption value at the 650nm place between 610-630nm, decomposition temperature height and decomposition curve are precipitous.Such metallo-chelate is applicable to that the laser recording wavelength is the NVD compact disc recordable recording layer material with ultra-resolution near-field structure of 650nm.
Claims (5)
1, a kind of metal azo inner complex, the name of this metal azo inner complex is called 2-(5-alkyl sulfenyl-1,3,4-thiadiazolyl group azo)-5-(N, the N-diethyl)-the trifluoromethyl sulfonanilide closes Ni, or Co, or Cu, or Zn, or Mn, be characterised in that its structural formula is as follows:
Wherein: C and N represent carbon and nitrogen respectively;
S and F represent sulphur and fluorine respectively;
R represents H, C
1-C
4Alkyl;
M
2+Be nickel, or cobalt, or copper, or zinc, or the manganese divalent-metal ion.
2, the preparation method of the described metal azo of claim 1 inner complex is characterized in that comprising the following steps:
1. diazotization reaction:
It is in 85% the phosphoric acid that diazo component is dissolved in an amount of concentration, ice bath is cooled to 0～5 ℃, under agitation with solid sodium nitrite, joined in the above-mentioned solution at 20-40 minute, the mol ratio of described Sodium Nitrite and diazo component is 1.05～1.10:1, stirring reaction 2 hours, if then illustrating, solution turned blue contains excessive nitrous acid, coupled reaction to next step is unfavorable, removes with urea, obtains the transparent diazotization solution of reddish-brown at last;
2. coupled reaction:
Mol ratio in coupling component and diazo component is the ratio weighing 3-(N of 1.1:1, N-diethyl amido) the trifluoromethyl sulfonanilide is made coupling component, coupling component and anhydrous sodium acetate be dissolved in the Erlenmeyer flask that fills anhydrous methanol form methanol solution, wherein: coupling component: anhydrous sodium acetate: the weight ratio of anhydrous methanol is 1:1:20, be cooled to 0～5 ℃ with ice bath, described diazotization solution was added drop-wise in the described methanol solution at 30-60 minute, fully stirring reaction is 3～10 hours, then add deionized water and continue stirring reaction more than 1 hour, after the standing over night, filter, washing, drying obtains azoic dyestuff
3. chelatropic reaction:
(a) get following raw materials by weight percent
Azoic dyestuff: 3-5wt%
Nickelous acetate, or cobaltous acetate, or zinc acetate, or venus crystals, or manganous acetate: 2-4wt%
Tetrahydrofuran (THF): 50-60wt%
Anhydrous methanol: 30-40wt%
Anhydrous sodium acetate: 3-7wt%
(b) azoic dyestuff is dissolved in forms tetrahydrofuran solution in the tetrahydrofuran (THF), with nickelous acetate or cobaltous acetate, or zinc acetate, or venus crystals, or manganous acetate is dissolved in the anhydrous methanol, in 20-60 ℃ of scopes, this methanol solution was joined in the described tetrahydrofuran solution in 20 minutes, reacted 5-10 hours;
(c) back that reacts completely adds water coolant, separates out crystal, and filtration, washing, drying obtain metal azo inner complex.
3, the preparation method of metal azo inner complex according to claim 2 is characterized in that described diazo component is 2-amino-5-methyl sulfenyl-1,3,4-thiadiazoles;
Or 2-amino-5-ethyl sulfenyl-1,3,4-thiadiazoles;
Or 2-amino-5-propyl group sulfenyl-1,3,4-thiadiazoles;
Or 2-amino-5-butyl sulfenyl-1,3,4-thiadiazoles;
Or 2-amino-5-thiohydroxy-1,3,4-thiadiazoles.
4, the preparation method of metal azo inner complex according to claim 2 is characterized in that described diazo component and concentration are that the weight ratio of 85% phosphoric acid is 20～30:1.
5,, be characterised in that the utilization of the medium of in ruddiness ultra-resolution near-field structure compact disc recordable, noting down according to claims 1 described azo-metal chelate.
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