CN1456555A - Isoxazole-azo-cyclohexanedione metal chelate and preparation method thereof - Google Patents
Isoxazole-azo-cyclohexanedione metal chelate and preparation method thereof Download PDFInfo
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- CN1456555A CN1456555A CN 03116629 CN03116629A CN1456555A CN 1456555 A CN1456555 A CN 1456555A CN 03116629 CN03116629 CN 03116629 CN 03116629 A CN03116629 A CN 03116629A CN 1456555 A CN1456555 A CN 1456555A
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- 239000013522 chelant Substances 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 38
- 238000005859 coupling reaction Methods 0.000 claims abstract description 25
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 25
- -1 4, 5-disubstituted isoxazole compounds Chemical class 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 230000008878 coupling Effects 0.000 claims abstract description 4
- 238000010168 coupling process Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 48
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 30
- 239000012954 diazonium Substances 0.000 claims description 19
- 150000001989 diazonium salts Chemical class 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical class O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 150000002545 isoxazoles Chemical class 0.000 claims description 7
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 159000000021 acetate salts Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000013500 data storage Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 abstract description 2
- 230000009920 chelation Effects 0.000 abstract 2
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexane-2,3-dione Chemical class CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 230000008859 change Effects 0.000 description 17
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 12
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 11
- 239000012453 solvate Substances 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- 230000000295 complement effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052752 metalloid Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 2
- CRKFVKCREBVZJP-UHFFFAOYSA-N 4-ethyl-5-methylbenzene-1,3-dicarboxylic acid Chemical compound CCC1=C(C)C=C(C(O)=O)C=C1C(O)=O CRKFVKCREBVZJP-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 2
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- 150000002085 enols Chemical group 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011175 product filtration Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
An isoxazole-azo-cyclohexanedione metal chelate and a preparation method thereof, wherein the isoxazole-azo-cyclohexanedione metal chelate is a 4, 5-disubstituted isoxazole-azo-1 ', 3' -cyclohexanedione metal chelate, and the structural general formula is : the diazotization reaction is carried out by carrying out diazotization reaction, coupling reaction and chelation reaction, wherein the diazotization reaction is carried out by 4, 5-disubstituted isoxazole compounds and sodium nitrite in a phosphoric acid system, and the reaction temperature is maintained at 0-5 ℃; the coupling reaction is carried out by diazo salt and 1 ', 3' -bade hexanedione compounds under the alkaline condition such as sodium hydroxide, the pH is = 10-14, and the reaction temperature is maintained at 0-5 ℃; the chelation reaction is carried out by coupling product and metal acetate in organic solvent at room temperature, and sodium alkoxide is used as catalyst. It has the advantages of short absorption wavelength, high solubility, high stability, etc. and may be used in new generation blue light recordable CD data storage medium matched with available 405nm blue light semiconductor laser.
Description
Technical field:
The present invention is relevant with the optical information memory technology, relates to a kind of isoxazole azo-group cyclohexanone analog metallo-chelate and preparation method thereof, is meant a kind of 4 ', 5 '-two substituted isoxazoles-azo-group-hydroresorcinol metalloid inner complex and preparation method thereof especially.Compound of the present invention has that absorbing wavelength is short, solubleness is big and stable advantages of higher, can be complementary with present 405nm blue-light semiconductor laser apparatus, can be used for blue light compact disc recordable data storage medium of new generation.
Background technology:
Optical storage media can be divided into inorganic optical storage media and organic optical storage media by attributive classification, and the former is made of inorganic materials such as tellurium-base alloy etc., and the latter is made of organic materials such as cyanine dyes, azoic dyestuff or phthalocyanine pigment etc.Studies show that, inorganic materials although also have sensitivity preferably and reading, and has realized commercialization as optical storage media, but there are compact disk structure and preparation method's complexity, thereby cause cost higher, and easily by air, moisture attack, shortcoming (reference: [1] Gu Donghong such as toxicity is bigger, Chen Qiying, Tang Xiaodong etc. Chinese laser, 1995,22 (7): 551-555; Reference: [2] Yao Zuguang. modern chemical industry, 1991,11 (2): 13-18).Compare with inorganic materials, organic materials has the storage density height, solubility property is good, cost of manufacture is low, environmental pollution is little, diamagnetic ability strong and structure is easy to processing, wavelength is easy to a series of advantages such as adjusting (reference: [3] S.R.Marder, B.Kippelen, A.K.Y.Jen etal.Nature, 1997,338 (6645): 845-851); Reference: [4] Young Jae Huh, Jong Sung Kim, Tae Young Nam et al.JpnJ.Appl.Phys., 1997,36 (1B): 403-409; Reference: [5] E.Hamada, T.Fujii, Y.Tomizawa et al.J.Appl.Phys., 1997,36 (1B): 593-594), therefore, adopt organic materials to be subjected to the common concern of countries in the world day by day as optical storage media, and one after the other drop into great amount of manpower and material resources and financial resources and study and compete, it is developed rapidly.
In recent years, the short wavelength laser research that high density compact disc is used has had development soon, is the realization of 405nm blue laser product as wavelength, makes the storage density of CD and storage speed obtain significantly to improve.Yet, can not meet generation so far with organic optical memory material that the 405nm blue laser is complementary, therefore seek novel and can will become current vital task with high performance organic optical memory material that the 405nm blue laser is complementary.
Metallo-chelate is the title complex that belongs to organic and inorganic joint, its structural formula is by the mode be combined into by coordinate bond or ionic linkage between metal ion and the organic ligand (molecule or ion), because its stability of structure, the complicacy of forming, the diversity of metal and ligand species, the adjustability of coordination environment, therefore, it is expected to become the system of seeking the potential application of tool in novel organic optical memory material.
Japanese Patent (reference: [6] Japan Patent No.2001-271001) once developed a kind of isoxazole-azo-group-beta-diketon metalloid inner complex, this compound can have remarkable absorption between 350nm～530nm, and thinks that it is expected to be used for blue light compact disc recordable data storage medium.But the preparation method of this compound has following shortcoming:
(1) in diazo process, adopts the nitrosyl sulfuric acid reaction system, and nitrosyl sulfuric acid is the severe corrosive fuming liquid with choke damp, so it is very high to conversion unit and requirement for experiment condition, the while nitrosyl sulfuric acid is deliquescence very easily, its deliquescence product is sulfuric acid, nitric acid and nitrogen protoxide, and nitrogen protoxide is poisonous, obnoxious flavour;
(2) owing to diazotization reaction needs carry out under 0-5 ℃ condition, and the activity of nitrosyl sulfuric acid is very high, easily produces a large amount of heat in moment in the aqueous solution, makes temperature of reaction control difficult relatively;
(3) because there is the cis-trans isomerization phenomenon in the structure of beta-diketon analog derivative, therefore in chelatropic reaction, very easily cause the generation of isomer, as the two part inner complexs of metal diketone (reference: the chief editor of organic chemistry teaching and research room of department of chemistry of Fudan University of [7] Lanzhou University, Experiment of Organic Chemistry＜second edition 〉, Higher Education Publishing House, 1994,192-196), thereby the reduction productive rate increases difficulty also for the separation purification of product.
Above-mentioned shortcoming has had a strong impact on the promotion and application of this method.
Summary of the invention:
The technical problem to be solved in the present invention is to overcome above-mentioned prior art problems, and a kind of 4 ', 5 '-two substituted isoxazoles-azo-group-hydroresorcinol metalloid inner complex and preparation method thereof is provided.
The general formula of molecular structure of 4 ', 5 '-two substituted isoxazoles of the present invention-azo-group-hydroresorcinol metalloid inner complex is as follows:
N in the structural formula represents nitrogen; R
1Or R
2Both can be identical also can be different, represent the straight or branched alkyl group of 1-10 carbonatomss such as hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl respectively; R
3Or R
4Both can be identical also can be different, represent the straight or branched alkyl group of 1～4 carbonatoms such as hydrogen, methyl, ethyl respectively; R
5Or R
6Both can be identical also can be different, represent the straight or branched alkyl group of 1～4 carbonatoms such as hydrogen, methyl, ethyl, sec.-propyl respectively, also can represent substituted aryl, as phenyl ring etc.; M represents metal, as nickel, copper, manganese, cobalt, chromium etc.
Of the present invention 4,5-two substituted isoxazoles-azo-group-1 ', 3 '-cyclohexyl diketone metallo-chelate is to get through diazotization reaction, coupled reaction and chelatropic reaction three steps, wherein diazotization reaction is by 4,5-two substituted isoxazoles compounds and Sodium Nitrite carry out in the phosphoric acid system, and temperature of reaction maintains 0～5 ℃; Coupled reaction is by diazonium salt and 1 ', 3 '-benzoylcyclohexandione under alkaline condition＜as sodium hydroxide carry out, pH=10～14, temperature of reaction maintains 0～5 ℃; Chelatropic reaction be by coupling product and metal acetate in organic solvent, as carrying out under tetrahydrofuran (THF) and the room temperature condition, adopt sodium alkoxide to make catalyzer, as sodium methylate.
Concrete synthesis step:
＜1〉diazotization reaction
3-An isoxazole compounds is joined in 85% phosphoric acid, and stirring and dissolving remains between 0-5 ℃ the temperature of system with ice bath, slowly adds the Sodium Nitrite solid then in above-mentioned system, and makes diazotization reaction complete.Wherein, the weight percent of 3-An isoxazole compounds, 85% phosphoric acid and Sodium Nitrite is respectively: 2.5%～4%: 94%～96%: 1.5%～2.5%.
＜2〉coupled reaction
The hydroresorcinol compounds is dissolved in the sodium hydroxide solution of pH=10-14, under 0-5 ℃, adds above-mentioned＜1 the prepared diazonium salt of step, and continue under 0-5 ℃, to react completely.Wherein, the weight percent of diazonium salt, hydroresorcinol compounds and sodium hydroxide solution is respectively: 0.5%～2%: 60%～75%: 25%～40%.
＜3〉chelatropic reaction
With above-mentioned＜2〉step synthetic azo-compound joins in the tetrahydrofuran (THF), stirs to make it dissolving.Add sodium alkoxide and the metal acetate salts solution that is dissolved in alcoholic solvent then respectively, and at room temperature stirring reaction is complete.Wherein, the weight percent of azo-compound, organic solvent, metal acetate salt, alcohols and sodium alkoxide is respectively: 2%～4%: 60%～70%: 1%～2%: 10%～20%: 10%～20%.
Above-mentioned said alcohol reagent is generally methyl alcohol or ethanol; Sodium alkoxide is a catalyzer, is generally sodium methylate or sodium ethylate, and it is by sodium Metal 99.5 and methyl alcohol or the direct hybrid reaction of ethanol and make.
4 of blue light absorption of the present invention, 5-two substituted isoxazoles-azo-group-1 ', the purposes of 3 '-cyclohexyl diketone metallo-chelate:
4,5-two substituted isoxazoles-azo-group-1 ', 3 '-cyclohexyl diketone metallo-chelate, the maximum absorption wavelength of its film is less than 450nm, solubleness in organic solvent is fit to spin coating legal system film greater than 3%, and stability is high, can be complementary with present 405nm blue-light semiconductor laser apparatus, be used for blue light compact disc recordable data storage medium of new generation.
Technique effect of the present invention is as follows:
1. diazotization reaction is carried out in the phosphoric acid system among the present invention, reaction system (the reference [8]: K.H.Sanders of this and weakly alkaline arylamine and nitrosyl sulfuric acid, R.L.Allen.Aromatic Diazo Components, 3rd ed.London:Edward Arnole (Publishers) Ltd., 1985,14-19) compare, reaction conditions is comparatively gentle, and this system matches with the back coupled reaction, make the coupled reaction heat release few, easy control of temperature has also been controlled simultaneously because highly acid diazonium salt joins the decomposition reaction that causes in the coupling system.
2. the present invention adopts hydroresorcinol analog derivative part and pure sodium catalyst, so has only the enol form isomery in its diketone structure, and there is not the cis-trans isomerization phenomenon, therefore, in chelatropic reaction, help the generation of target product, and can not cause that other isomer or by product produce.
3. no poisonous, obnoxious flavour generation in the preparation method's of the present invention reaction process, conversion unit there is not particular requirement, advantage such as productive rate height and catalyzer source is easy to get, and is simple for production, preparation method of the present invention both had been suitable for prepared in laboratory, also can be fit to suitability for industrialized production.
4. the maximum absorption spectrum of metallo-chelate film of the present invention is positioned at royal purple light district, can be complementary with present 405nm blue-light semiconductor laser apparatus to be used for blue light compact disc recordable data storage medium of new generation.
Description of drawings:
Fig. 1: 2-(5 '-methyl-3 '-azo-group isoxazole)-5, the 5-dimethyl-abosrption spectrogram of hydroresorcinol copper chelate in film
Fig. 2: 2-(5 '-tertiary butyl-3 '-azo-group isoxazole)-5, the 5-dimethyl-abosrption spectrogram of hydroresorcinol copper chelate in film
Embodiment:
Enumerate embodiment below, the present invention is elaborated, but should not limit protection scope of the present invention.
Embodiment 1:
2-(5 '-methyl-3 '-azo-group isoxazole)-5,5-dimethyl-hydroresorcinol copper chelate synthetic
＜1〉diazotization reaction
5-methyl-3-An isoxazole compound is joined in 85% phosphoric acid, and stirring and dissolving remains between 0-5 ℃ the temperature of system with ice bath, slowly adds the Sodium Nitrite solid then in above-mentioned system, and makes diazotization reaction complete.Wherein, 5-methyl-3-An isoxazole compound, the weight percent between 85% phosphoric acid and the Sodium Nitrite is respectively: 2.5%: 95.5%: 2%.
＜2〉coupled reaction
With 5,5-dimethyl-hydroresorcinol is dissolved in the aqueous sodium hydroxide solution of pH=10, under 0-5 ℃, adds above-mentioned＜1〉the prepared diazonium salt solution of step, and continue under 0-5 ℃, to react completely.Reaction product is filtered, washing, and filter cake obtains flaxen crystallized product through recrystallization.Wherein, 5,5-dimethyl-hydroresorcinol, the weight percent between aqueous sodium hydroxide solution and the diazonium salt is respectively: 1%: 73%: 26%.Productive rate: 52%.
＜3〉chelatropic reaction
With above-mentioned＜2〉step synthetic azo-compound joins in the tetrahydrofuran (THF) organic solvent, stirs to make it dissolving.Adding is dissolved in the neutralized verdigris solution of methanol solvate and 0.5% sodium methoxide solution then, and at room temperature stirring reaction is complete.Reaction product filtration, washing, the dry yellow solid that gets.Wherein, azo-compound, tetrahydrofuran (THF), neutralized verdigris, the weight percent of methanol solvate and 0.5% sodium methylate is respectively: 4%: 63%: 1.5%: 15%: 16.5%.Productive rate: 75%.
Embodiment 2:
2-(5 '-tertiary butyl-3 '-azo-group isoxazole)-5,5-dimethyl-hydroresorcinol copper chelate synthetic
＜1〉diazotization reaction
Raw material and step are with embodiment 1, and different is to change 5-methyl-3-An isoxazole into the 5-tertiary butyl-3-An isoxazole; The 5-tertiary butyl-3-An isoxazole: 85% phosphoric acid: the weight percent between the Sodium Nitrite changes into respectively: 2.5%: 96%: 1.5%.
＜2〉coupled reaction
Step is with embodiment 1, and different is to change the pH value into 12; 5,5-dimethyl-hydroresorcinol: aqueous sodium hydroxide solution: the weight percent between the diazonium salt changes into respectively: 1.5%: 70%: 28.5%.Productive rate is 53%.
＜3〉chelatropic reaction
Step is with embodiment 1, and different is with azo-compound: tetrahydrofuran (THF): neutralized verdigris: methanol solvate: the weight percent of 0.5% sodium methylate changes into respectively: 5%: 65%: 1%: 12%: 17%.Productive rate is 84%.
Embodiment 3:
2-(4 ', 5 '-dimethyl-3 '-azo-group isoxazole)-5,5-dimethyl-hydroresorcinol nickel chelate synthetic
＜1〉diazotization reaction
The same embodiment of step＜1 〉, different is to change 5-methyl-3-An isoxazole compound into 4,5-dimethyl-3-An isoxazole compound; 4,5-dimethyl-3-An isoxazole: 85% phosphoric acid: the weight percent between the Sodium Nitrite changes into respectively: 3%: 95.5%: 1.5%.
＜2〉coupled reaction
Step is with embodiment 1, and different is to change the pH value into 12; 5,5-dimethyl-hydroresorcinol: aqueous sodium hydroxide solution: the weight percent between the diazonium salt changes into respectively: 2.5%: 60%: 38.5%.Productive rate is 54%.
＜3〉chelatropic reaction
Step is with embodiment 1, and different is to change neutralized verdigris into nickel acetate; 0.5% sodium methylate changes 0.7% sodium methylate into; Azo-compound: tetrahydrofuran (THF): nickel acetate: methanol solvate: the weight percent of 0.7% sodium methylate changes into respectively: 3%: 65%: 2%: 10%: 20%.Productive rate is 84%.
Embodiment 4:
Synthesizing of 2-(5 '-ethyl-3 '-azo-group isoxazole)-5-ethyl-hydroresorcinol manganic chelates
＜1〉diazotization reaction
The same embodiment of step＜1 〉, different is to change 5-methyl-3-An isoxazole compound into 5-ethyl-3-An isoxazole; 5-ethyl-3-An isoxazole: 85% phosphoric acid: the weight percent between the Sodium Nitrite changes into respectively: 3.5%: 94.5%: 2%.
＜2〉coupled reaction
Step is with embodiment 1, and different is with 5, and 5-dimethyl-hydroresorcinol changes 5-ethyl-hydroresorcinol into; The pH value changes 14 into; 5-ethyl-hydroresorcinol: aqueous sodium hydroxide solution: the weight percent between the diazonium salt changes into respectively: 0.5%: 74.5%: 25%.Productive rate is 45%.
＜3〉chelatropic reaction
Step is with embodiment 1, and different is to change neutralized verdigris into manganese acetate; 0.5% sodium methylate changes 1% sodium ethylate into; Methyl alcohol changes ethanol into; Azo-compound: tetrahydrofuran (THF): manganese acetate: alcohol solvent: the weight percent of 1% sodium ethylate changes into respectively: 3%: 60%: 2%: 10%: 25%.Productive rate is 76%.
Embodiment 5
Synthesizing of 2-(5 '-methyl-3 '-azo-group isoxazole)-5-(to N, the N-3,5-dimethylphenyl)-hydroresorcinol copper chelate
1〉diazotization reaction
The same embodiment of step＜1 〉, different is with 5-methyl-3-An isoxazole compound: 85% phosphoric acid: the weight percent between the Sodium Nitrite changes into respectively: 3%: 95%: 2%.
＜2〉coupled reaction
Step is with embodiment 1, and different is with 5, and 5-dimethyl-hydroresorcinol changes 5-(to N, the N-3,5-dimethylphenyl)-hydroresorcinol into; The pH value changes 14 into; 5-(to N, the N-3,5-dimethylphenyl)-hydroresorcinol: aqueous sodium hydroxide solution: the weight percent between the diazonium salt changes into respectively: 2%: 70%: 28%.Productive rate is 56%.
＜3〉chelatropic reaction
Step is with embodiment 1, and different is to change 0.5% sodium methylate into 1% sodium methylate; Azo-compound: tetrahydrofuran (THF): neutralized verdigris: methanol solvate: the weight percent of 1% sodium methylate changes into respectively: 5%: 60%: 2%: 13%: 20%.Productive rate is 82%.
Embodiment 6
Synthesizing of 2-(5 '-tertiary butyl-3 '-azo-group isoxazole)-5-(to N, the N-3,5-dimethylphenyl)-hydroresorcinol copper chelate
1〉diazotization reaction
Step is with embodiment 1, and different is to change 5-methyl-3-An isoxazole compound into the 5-tertiary butyl-3-An isoxazole compound; The 5-tertiary butyl-3-An isoxazole: 85% phosphoric acid: the weight percent between the Sodium Nitrite changes into respectively: 4%: 94.5%: 1.5%.
＜2〉coupled reaction
Step is with embodiment 1, and different is with 5, and 5-dimethyl-hydroresorcinol changes 5-(to N, the N-3,5-dimethylphenyl)-hydroresorcinol into; The pH value changes 14 into; 5-(to N, the N-3,5-dimethylphenyl)-hydroresorcinol: aqueous sodium hydroxide solution: the weight percent between the diazonium salt changes into respectively: 1.5%: 75%: 23.5%.Productive rate is 56%.
＜3〉chelatropic reaction
Step is with embodiment 1, and different is to change 0.5% sodium methylate into 1% sodium methylate; Azo-compound: tetrahydrofuran (THF): neutralized verdigris: methanol solvate: the weight percent of 1% sodium methylate changes into respectively: 2%: 65%: 1%: 14%: 18%.Productive rate is 82%.
Embodiment 7
2-(5 '-sec.-propyl-3 '-azo-group isoxazole)-4,4-dimethyl-hydroresorcinol cobalt chelates synthetic
1〉diazotization reaction
Step is with embodiment 1, and different is to change 5-methyl-3-An isoxazole compound into 5-sec.-propyl-3-An isoxazole compound; 5-sec.-propyl-3-An isoxazole: 85% phosphoric acid: the weight percent between the Sodium Nitrite changes into respectively: 3%: 94.5%: 2.5%.
＜2〉coupled reaction
Step is with embodiment 1, and different is with 5, and 5-dimethyl-hydroresorcinol changes 4 into, 4-dimethyl-hydroresorcinol; The pH value changes 14 into; 4,4-dimethyl-hydroresorcinol: aqueous sodium hydroxide solution: the weight percent between the diazonium salt changes into respectively: 1.5%: 73%: 26.5%.Productive rate is 51%.
＜3〉chelatropic reaction
Step is with embodiment 1, and different is to change neutralized verdigris into Cobaltous diacetate; Azo-compound: tetrahydrofuran (THF): Cobaltous diacetate: methanol solvate: the weight percent of 0.5% sodium methylate changes into respectively: 4%: 65%: 1.5%: 15.5%: 14%.Productive rate is 80%.
Embodiment 8
Synthesizing of 2-(4 ', 5 '-diethyl-3 '-azo-group isoxazole)-5-sec.-propyl-hydroresorcinol chromium complex
＜1〉diazotization reaction
Step is with embodiment 1, and different is to change 5-methyl-3-An isoxazole compound into 4,5-diethyl-3-An isoxazole compound; 4,5-diethyl-3-An isoxazole: 85% phosphoric acid: the weight percent between the Sodium Nitrite changes into respectively: 2.5%: 95%: 2.5%.
＜2〉coupled reaction
Step is with embodiment 1, and different is with 5, and 5-dimethyl-hydroresorcinol changes 5-sec.-propyl-hydroresorcinol into; The pH value changes 14 into; 5-sec.-propyl-hydroresorcinol: aqueous sodium hydroxide solution: the weight percent between the diazonium salt changes into respectively: 1.5%: 68.5%: 30%.Productive rate is 39%.
＜3〉chelatropic reaction
Step is with embodiment 1, and different is to change neutralized verdigris into chromium acetate; Azo-compound: tetrahydrofuran (THF): chromium acetate: methanol solvate: the weight percent of 0.5% sodium methylate changes into respectively: 3.4%: 63%: 1.6%: 15%: 17%.Productive rate is 47%.
Embodiment 9
Synthesizing of 2-(5 '-methyl-3 '-azo-group isoxazole)-5-(3 ', 4 '-Dimethoxyphenyl)-hydroresorcinol copper chelate
＜1〉diazotization reaction
Step is with embodiment 1, and different is with 5-methyl-3-An isoxazole compound: 85% phosphoric acid: the weight percent between the Sodium Nitrite changes into respectively: 3%: 95.5%: 1.5%.
＜2〉coupled reaction
Step is with embodiment 1, and different is with 5, and 5-dimethyl-hydroresorcinol changes 5-(3 ', 4 '-Dimethoxyphenyl)-hydroresorcinol into; The pH value changes 14 into; 5-(3 ', 4 '-Dimethoxyphenyl)-hydroresorcinol: aqueous sodium hydroxide solution: the weight percent between the diazonium salt changes into respectively: 2%: 70%: 28%.Productive rate is 51%.
＜3〉chelatropic reaction
Step is with embodiment 1, and different is to change 0.5% sodium methylate into 1% sodium ethylate; Methyl alcohol changes ethanol into; Azo-compound: tetrahydrofuran (THF): neutralized verdigris: methanol solvate: the weight percent of 1% sodium methylate changes into respectively: 3.5%: 70%: 1%: 20%: 5.5%.Productive rate is 55%.
Embodiment 10
2-(5 '-methyl-3 '-azo-group isoxazole)-4,5-dimethyl-hydroresorcinol copper chelate synthetic
＜1〉diazotization reaction
Step is with embodiment 1, and different is with 5-methyl-3-An isoxazole: 85% phosphoric acid: the weight percent between the Sodium Nitrite changes into respectively: 3%: 95.5%: 1.5%.
＜2〉coupled reaction
Step is with embodiment 1, and different is with 5, and 5-dimethyl-hydroresorcinol changes 4 into, 5-dimethyl-hydroresorcinol; The pH value changes 14 into; 4,5-dimethyl-hydroresorcinol: aqueous sodium hydroxide solution: the weight percent between the diazonium salt changes into respectively: 2%: 68%: 30%.Productive rate is 51%.
＜3〉chelatropic reaction
Step is with embodiment 1, and different is to change 0.5% sodium methylate into 1% sodium ethylate; Methyl alcohol changes ethanol into; Azo-compound: tetrahydrofuran (THF): neutralized verdigris: methanol solvate: the weight percent of 1% sodium methylate changes into respectively: 3.5%: 65%: 1.5%: 15%: 15%.Productive rate is 55%.
Embodiment 11
2-(5 '-methyl-3 '-azo-group isoxazole)-4-ethyl-5-methyl isophthalic acid, hydroresorcinol copper chelate synthetic
＜1〉diazotization reaction
Step is with embodiment 1, and different is with 5-methyl-3-An isoxazole: 85% phosphoric acid: the weight percent between the Sodium Nitrite changes into respectively: 3%: 95.5%: 1.5%.
＜2〉coupled reaction
Step is with embodiment 1, and different is with 5, and 5-dimethyl-hydroresorcinol changes 4-ethyl-5-methyl isophthalic acid, hydroresorcinol into; The pH value changes 14 into; 4-ethyl-5-methyl isophthalic acid, hydroresorcinol: aqueous sodium hydroxide solution: the weight percent between the diazonium salt changes into respectively: 1%: 70%: 29%.Productive rate is 51%.
＜3〉chelatropic reaction
Step is with embodiment 1, and different is to change 0.5% sodium methylate into 1% sodium ethylate; Methyl alcohol changes ethanol into; Azo-compound: tetrahydrofuran (THF): neutralized verdigris: methanol solvate: the weight percent of 1% sodium methylate changes into respectively: 3.5%: 60%: 1%: 17%: 18.5%.Productive rate is 55%.
Embodiment 12
The sample (embodiment 1 sample) of 30mg is dissolved in the C3-Fluoroalcohol of 1ml, adopts spin-coating method to be coated on equably on the K9 sheet glass, treat promptly to get stable film after the solvent evaporates.The maximum absorption wavelength of this film is 371nm, sees Fig. 1, is expected to be complementary with present 405nm blue-light semiconductor laser apparatus.
Embodiment 13
The sample (embodiment 2 samples) of 30mg is dissolved in the C3-Fluoroalcohol of 1ml, adopts spin-coating method to be coated on equably on the K9 sheet glass, treat promptly to get stable film after the solvent evaporates.The maximum absorption wavelength of this film is 369nm, sees Fig. 2, is expected to be complementary with present 405nm blue-light semiconductor laser apparatus.
Claims (5)
1. isoxazole-azo-group-cyclohexyl diketone metallo-chelate; this isoxazole-azo-group-cyclohexyl diketone metallo-chelate is 4,5-two substituted isoxazoles-azo-group-1 ', 3 '-cyclohexyl diketone metallo-chelate is characterized in that its structural formula has following general formula:
In the structural formula:
N represents nitrogen;
R
1Or R
2Both can be identical also can be different, represent the straight or branched alkyl group of 1-10 carbonatomss such as hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl respectively;
R
3Or R
4Both can be identical also can be different, represent the straight or branched alkyl group of 1～4 carbonatoms such as hydrogen, methyl, ethyl respectively;
R
5Or R
6Both can be identical also can be different, represent the straight or branched alkyl group of 1～4 carbonatoms such as hydrogen, methyl, ethyl, sec.-propyl respectively, also can represent substituted aryl, as phenyl ring;
M represents metal, as nickel, copper, manganese, cobalt, chromium.
2, according to claim 14,5-two substituted isoxazoles-azo-group-1 ', the preparation method of 3 '-cyclohexyl diketone metallo-chelate, it is characterized in that it makes through diazotization reaction, coupled reaction and chelatropic reaction, wherein diazotization reaction is by 4,5-two substituted isoxazoles compounds and Sodium Nitrite carry out in the phosphoric acid system, and temperature of reaction maintains 0～5 ℃; Coupled reaction is by diazonium salt and 1 ', 3 '-benzoylcyclohexandione under alkaline condition＜as sodium hydroxide carry out, pH=10～14, temperature of reaction maintains 0～5 ℃; Chelatropic reaction is carried out in organic solvent He under the room temperature condition by coupling product and metal acetate, adopts sodium alkoxide to make catalyzer.
3, according to claim 24,5-two substituted isoxazoles-azo-group-1 ', the preparation method of 3 '-cyclohexyl diketone metallo-chelate is characterized in that its concrete synthesis step is:
＜1〉diazotization reaction
3-An isoxazole compounds is joined in 85% phosphoric acid, stirring and dissolving, with ice bath the temperature of system is remained between 0-5 ℃, slowly add the Sodium Nitrite solid then in above-mentioned system, and make diazotization reaction complete, wherein, the weight percent of 3-An isoxazole compounds, 85% phosphoric acid and Sodium Nitrite is respectively: 2.5%～4%: 94%～96%: 1.5%～2.5%;
＜2〉coupled reaction
The hydroresorcinol compounds is dissolved in the sodium hydroxide solution of pH=10-14, under 0-5 ℃, adds above-mentioned＜1 the prepared diazonium salt of step, and continue under 0-5 ℃, to react completely.Wherein, the weight percent of diazonium salt, hydroresorcinol compounds and sodium hydroxide solution is respectively: 0.5%～2%: 60%～75%: 25%～40%;
＜3〉chelatropic reaction
With above-mentioned＜2〉step synthetic azo-compound joins in the tetrahydrofuran (THF), stirs to make it dissolving, and add sodium alkoxide then respectively and be dissolved in the metal acetate salts solution of alcoholic solvent, and at room temperature stirring reaction is complete; Wherein, the weight percent of azo-compound, organic solvent, metal acetate salt, alcohols and sodium alkoxide is respectively: 2%～4%: 60%～70%: 1%～2%: 10%～20%: 10%～20%.
4, according to claim 34,5-two substituted isoxazoles-azo-group-1 ', the preparation method of 3 '-cyclohexyl diketone metallo-chelate is characterized in that described alcoholic solvent is methyl alcohol or ethanol.
5, according to claim 34,5-two substituted isoxazoles-azo-group-1 ', the preparation method of 3 '-cyclohexyl diketone metallo-chelate is characterized in that said catalyzer sodium alkoxide is sodium methylate or sodium ethylate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007007748A1 (en) * | 2005-07-14 | 2007-01-18 | Mitsubishi Kagaku Media Co., Ltd. | Optical recording medium, optical recording material and metal complex compound |
| CN105385186A (en) * | 2015-10-19 | 2016-03-09 | 广州市纬庆化工科技有限公司 | Migration-resistant red dye, preparation method therefor and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007007748A1 (en) * | 2005-07-14 | 2007-01-18 | Mitsubishi Kagaku Media Co., Ltd. | Optical recording medium, optical recording material and metal complex compound |
| US8075976B2 (en) | 2005-07-14 | 2011-12-13 | Mitsubishi Kagaku Media Co., Ltd. | Optical recording medium, optical recording material and metal complex compound |
| US8309196B2 (en) | 2005-07-14 | 2012-11-13 | Mitsubishi Kagaku Media Co., Ltd. | Optical recording medium, optical recording material and metal complex compound |
| CN101238182B (en) * | 2005-07-14 | 2013-09-11 | 三菱化学媒体株式会社 | Optical recording medium, optical recording material and metal complex compound |
| CN105385186A (en) * | 2015-10-19 | 2016-03-09 | 广州市纬庆化工科技有限公司 | Migration-resistant red dye, preparation method therefor and application thereof |
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