CN106280534A - A kind of orchil compound and preparation method thereof - Google Patents
A kind of orchil compound and preparation method thereof Download PDFInfo
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- CN106280534A CN106280534A CN201610666293.6A CN201610666293A CN106280534A CN 106280534 A CN106280534 A CN 106280534A CN 201610666293 A CN201610666293 A CN 201610666293A CN 106280534 A CN106280534 A CN 106280534A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 75
- 239000004218 Orcein Substances 0.000 title claims abstract description 18
- 235000019248 orcein Nutrition 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000009833 condensation Methods 0.000 claims abstract description 32
- 230000005494 condensation Effects 0.000 claims abstract description 32
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005859 coupling reaction Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 6
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 claims abstract 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 235000010288 sodium nitrite Nutrition 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- -1 anilino- Chemical class 0.000 claims description 18
- 238000006482 condensation reaction Methods 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 claims description 14
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims description 14
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 5
- 229910006069 SO3H Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- 238000010612 desalination reaction Methods 0.000 abstract description 27
- 238000001914 filtration Methods 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 11
- 230000008878 coupling Effects 0.000 abstract description 8
- 238000010168 coupling process Methods 0.000 abstract description 8
- 239000012954 diazonium Substances 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract description 3
- 230000007423 decrease Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 32
- 239000007788 liquid Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 31
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- 239000000975 dye Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 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 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical compound O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000011118 depth filtration Methods 0.000 description 3
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000985 reactive dye Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 2
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical group CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229950000244 sulfanilic acid Drugs 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZAOCWQZQPKGTRN-UHFFFAOYSA-N nitrous acid;sodium Chemical compound [Na].ON=O ZAOCWQZQPKGTRN-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- JGIGXKSJLSQJGQ-UHFFFAOYSA-K trisodium 5-[[4-chloro-6-(N-methylanilino)-1,3,5-triazin-2-yl]amino]-4-hydroxy-3-[(2-sulfonatophenyl)diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].CN(c1ccccc1)c1nc(Cl)nc(Nc2cc(cc3cc(c(N=Nc4ccccc4S([O-])(=O)=O)c(O)c23)S([O-])(=O)=O)S([O-])(=O)=O)n1 JGIGXKSJLSQJGQ-UHFFFAOYSA-K 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
- C09B29/0007—Monoazo dyes prepared by diazotising and coupling from diazotized anilines containing acid groups, e.g. CO2H, SO3H, PO3H2, OSO3H, OPO2H2; Salts thereof
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/24—Monoazo dyes prepared by diazotising and coupling from coupling components containing both hydroxyl and amino directing groups
- C09B29/28—Amino naphthols
- C09B29/30—Amino naphtholsulfonic acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of orchil compound and preparation method thereof, the preparation method of this Ink-jet dye compound comprises the steps: that (1) H-acid in acid condition is condensed with Cyanuric Chloride, uses filter paper filtering after condensation；(2) it is SO by compound wherein R3H, carries out diazonium and condensation substance coupling；(3) by compound B1Join and above-mentioned solution carries out secondary condensation；(4) add quantitative activated carbon and kieselguhr processes, then desalination and concentration；(5) concentrated solution being carried out acidic hydrolysis, desalination and concentration obtains required compound the most again.Utilizing the product that technical scheme synthesizes, purity is high, and dissolubility is good, and stability is high, simple to operate, easily amplifies production.Compare more conventional synthesis mode, it is not necessary to the purity that just can reach the highest of saltouing, decrease the yield of waste water, improve production efficiency, saved cost.There is good promotion prospect.
Description
Technical field
The present invention relates to technical field of dye, especially relate to a kind of orchil compound and preparation method thereof.
Background technology
Red ink-jet dye in the market, great majority are activity orchil, such as: active red 180, active red
195, active red 141 some row dyestuffs such as grade.Because these dyestuffs are all reactive dye, have during using and much ask
Topic, such as: pH value is unstable, the coloured light problem etc. of color.And red great majority used currently on the market are magenta, and
It not that gold-tinted is red.
Along with the continuous progress of printer technology, the classification of ink-jet ink is thinner, particularly wide format printer.
The ink of color printer has four colors, six colors, seven colors, 12 colors etc. now.The kind of the ink image printed more
Add clear distinctness.But the gold-tinted redness in printer is substantially based on colorant match, it is to be mixed by pinkish red and two kinds of colors of yellow
Being combined into large red, Ye You company Reactive Red 24 replaces, but owing to being reactive dye, equally deposits with traditional reactive dye
In problems such as pH value instability.
Summary of the invention
In view of this, the invention provides compound and the synthetic method thereof of a kind of orchil, the dye that the present invention provides
Material purity is high, and color is vivid, and filterability is good, and pH is stable, good stability.
In order to realize foregoing invention purpose, the present invention provides techniques below scheme:
The invention provides a kind of orchil compound with structure shown in Formulas I:
Wherein R is SO3H, B be: anilino-, methylphenylamine base, N-ethylaniline base, o ethyl aniline base, adjacent methyl
One in anilino-.
The invention provides the preparation method of the dye composition described in technique scheme with Formulas I structure, including such as
Lower step:
(1) Cyanuric Chloride and the H-acid with structure shown in Formula II are carried out condensation reaction, obtain structure as shown in formula III
Compound:
(2) compound with structure shown in formula IV is carried out diazo-reaction in an hcl ambient with sodium nitrite, obtain
There is structure diazenium compound shown in Formula V:
(3) tool that the diazenium compound with Formula V structure described step (2) obtained and described step (1) obtain
The compound having structure shown in formula III carries out coupling reaction, obtains structural compounds shown in Formula IV:
(4) compound with structure shown in Formula IV that aniline or anil and described step (5) obtain is carried out
Secondary condensation, obtains the compound with structure shown in Formula VII:
(5) shown in the Formula VII described step (4) obtained, the compound of structure is hydrolyzed in acid condition, obtains
The compound of structure shown in Formulas I；
Not free order between described step (1) and step (2).
Preferably, in step (1), the temperature of condensation reaction is 0～5 DEG C, and the time of condensation reaction is 1～2h；Condensation reaction
Carry out under conditions of pH value is 5.5～7.
Preferably, the diazo reaction temperature in step (2) is 5～15 DEG C, and the diazo reaction time is 0.8～1.2h；Diazonium
Reaction is carried out under conditions of pH value is 6～7.
Preferably, in described step (3), couple temperature is 5～15 DEG C, and Coupling time is 0.8～1.2h；Coupling reaction exists
PH value is to carry out under conditions of 6～7.
Preferably, in described step (4), secondary condensation temperature is 15～30 DEG C, and the secondary condensation time is 1.5～2.5h；Two
Secondary condensation reaction is carried out under conditions of pH value is 6.3～7.5.
In step (5), hydrolysis temperature is 85～97 DEG C, and hydrolysis time is 3.5～4.5h；Hydrolysis is at the bar that pH value is 1～2
Carry out under part.
In step (1), Cyanuric Chloride is 1.03～1.5:1 with the mol ratio of the H-acid with structure shown in Formula II；
The mol ratio of the compound with structure shown in formula IV described in step (2) and sodium nitrite be 1:1.03～
1.5；
The diazenium compound with Formula V structure described in step (3) with there is rubbing of structural compounds shown in Formula II
That ratio is 1:1.03～1.5；
What the aniline described in step (4) or anil and described step (5) obtained has structure shown in Formula IV
The mol ratio of compound is 1.05～1.5:1.
In step (4), anil is methylphenylamine, N-ethylaniline, and o ethyl aniline, in o-toluidine
A kind of.
Advantageous Effects: the invention provides the orchil compound with structure shown in Formulas I, dyestuffs purity is high,
Color is vivid, and filterability is good, pH and Heat stability is good；
Present invention also offers the preparation method of orchil compound described in technique scheme, with existing synthesis side
Method is compared, and the preparation method building-up process that the present invention provides is simple；The purity of synthesis afterproduct is high, eliminates that to be conventionally synthesized be salt
The step of analysis, decreases the discharge of waste water；Hydrolysis acidic hydrolysis, solves in basic hydrolysis, the problem that by-product is many；Close
The finished product become out is stable more preferable with conventional synthesis process synthesis；Make product more competitive superiority.Test result indicate that the present invention
The orchil compound fluency provided is good, coloured light, pH and Heat stability is good, and purity is high.
Accompanying drawing illustrates:
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described in further detail:
Fig. 1: the orchil liquid chromatogram of conventional method synthesis disclosed in prior art；
The orchil liquid chromatogram of synthesis in Fig. 2: embodiment 1；
The orchil liquid chromatogram of synthesis in Fig. 3: embodiment 2；
The orchil liquid chromatogram of synthesis in Fig. 4: embodiment 3.
Detailed description of the invention
The invention provides a kind of orchil compound with structure shown in Formulas I:
Wherein R is SO3H, B be: anilino-, methylphenylamine base, N-ethylaniline base, o ethyl aniline base, adjacent methyl
One in anilino-.
Described orchil compound is preferably:
Present invention also offers the preparation method of the dye composition described in technique scheme with structure shown in Formulas I,
Comprise the steps:
(1) Cyanuric Chloride and the H-acid with structure shown in Formula II are carried out condensation reaction, obtain structure as shown in formula III
Compound:
(2) compound with structure shown in formula IV is carried out diazo-reaction in an hcl ambient with sodium nitrite, obtain
There is structure diazenium compound shown in Formula V:
(3) tool that the diazenium compound with Formula V structure described step (2) obtained and described step (1) obtain
The compound having structure shown in formula III carries out coupling reaction, obtains structural compounds shown in Formula IV:
(4) compound with structure shown in Formula IV that aniline or anil and described step (5) obtain is carried out
Secondary condensation, obtains the compound with structure shown in Formula VII:
(5) shown in the Formula VII described step (4) obtained, the compound of structure is hydrolyzed in acid condition, obtains
The compound of structure shown in Formulas I；
Not free order between described step (1) and step (2).
Cyanuric Chloride and the H-acid with structure shown in Formula II are carried out condensation reaction by the present invention, obtain having shown in formula III
The compound of structure.H-acid is preferably dissolved by the present invention, obtains H-acid solution；Cyanuric Chloride is disperseed, obtains Cyanuric Chloride dispersion
Liquid；Described H-acid solution is added drop-wise in Cyanuric Chloride dispersion liquid, carries out condensation reaction.
In the present invention, H-acid is preferably distributed in water by described H-acid solution, adjusts pH value with alkali, makes H-acid all dissolve
Obtain.In the present invention, the mass concentration of described H-acid solution is preferably 10～15%；Described alkali is preferably sodium hydroxide or hydrogen
Lithium oxide, more preferably sodium hydroxide；The concentration of described alkali is 15～25%, preferably 20%；The pH value of described H-acid solution is excellent
Elect 6～6.5 as.
In the present invention, Cyanuric Chloride is preferably distributed in frozen water by described Cyanuric Chloride dispersion liquid, and making beating obtains.At this
In invention, the mass concentration of described Cyanuric Chloride dispersion liquid is preferably 8～12%；The time of described making beating be preferably 20～
40min；More preferably 30min.
In the present invention, rate of addition changes into: about the 1% of dropping total amount per minute, time for adding controls at 1.5-2 little
Time.In the present invention, the temperature of described condensation reaction is preferably 0～5 DEG C, more preferably 0～3 DEG C；Described condensation reaction time
Between be preferably 1～2h, more preferably 1.5 hours；Described condensation reaction is preferably carried out under conditions of pH value preferably 5.5～7,
More preferably 6～6.5.In the present invention, the pH value of described condensation reaction is preferably regulated by alkali compounds, described alkalization
Compound is preferably sodium bicarbonate.
In the present invention, described Cyanuric Chloride with have the mol ratio of H-acid of structure shown in Formula II for preferably 1.03～
1.5:1, more preferably 1.03～1.3:1.
After being condensed, the present invention preferably filters the reactant liquor of described condensation reaction, removes unreacted Cyanuric Chloride,
To having the compound condensation liquid of structure shown in formula III, standby.In the present invention, described filtration preferably employs Medium speed filter paper and enters
OK.
The compound with structure shown in formula IV is carried out diazo-reaction with sodium nitrite by the present invention in an hcl ambient,
Obtain having structure diazenium compound shown in Formula V.In described Formula V, R is preferably-SO3H；In the present invention, described R replaces tool
Body is ortho position, para-position or meta replace.
The present invention preferably by the compound dissolution of structure shown in formula IV, obtains the solution of compound shown in formula IV；By nitrous
Acid sodium joins in the solution of compound shown in described formula IV, obtains mixed solution；Described mixed solution is added drop-wise to hydrochloric acid with
In the mixed liquor of frozen water, carry out diazo-reaction, obtain the diazonium compound with Formula V locking-type structure.The present invention preferably will tool
Having the compound dissolution of formula IV structure in water, first adjust pH value with alkali, described alkali is preferably sodium hydroxide, and described pH value is preferred
It is 6～6.5.
In the present invention, described mixed solution is added drop-wise to hydrochloric acid with the speed in the mixed liquor of frozen water preferably ....?
In the present invention, the temperature of described diazo-reaction is preferably 5～15 DEG C, more preferably 5～10 DEG C；Described diazo-reaction time
Between be preferably 0.8～1.2h, more preferably 1h；Described diazo-reaction is preferably carried out under conditions of pH value is 6～7, more excellent
Elect 6～6.5 as.
In the present invention, the mol ratio of the described compound and sodium nitrite with structure shown in formula IV is preferably 1:
1.03～1.5, more preferably 1:1.03～1.3；
After described diazo-reaction, the present invention preferably removes the sodium nitrite of excess, obtains the weight with structure shown in Formula V
Nitrogen salt compound.In the present invention, described sodium nitrite is preferably removed by solid sulfamic acid, concrete, to described diazonium
Change the sodium nitrite adding solid sulfamic acid removing excess in the reactant liquor that reaction obtains.The use of described solid sulfamic acid
Amount is the 0.1% of sodium nitrite addition quality.
After obtaining the compound of structure shown in formula III and formula IV, the diazonium salinization with Formula V structure that the present invention will obtain
Compound carries out coupling reaction with the compound with structure shown in formula III obtained, and obtains the compound of structure shown in Formula IV.
The diazenium compound obtained preferably is added directly in the condensation solution that above-mentioned filtration is good and reacts by the present invention, is had
There is the conjugates feed liquid of structure shown in Formula IV.
The temperature of heretofore described coupling reaction is preferably 5～15 DEG C, more preferably 5～10 DEG C；Described coupling reaction
Time is preferably 0.8～1.2h, more preferably 1h；The pH of described coupling reaction is preferably 6～7, more preferably 6～6.5.?
In the present invention, the described diazenium compound with Formula V structure is preferred with the mol ratio with structural compounds shown in formula III
For 1:1.03～1.5, more preferably 1:1.03～1.3.
After obtaining the compound of structure shown in Formula IV, the present invention by aniline or anil with there is structure shown in Formula IV
Compound carry out secondary condensation, obtain the compound with structure shown in Formula VII.The present invention is preferably by aniline or aniline derivatives
Thing joins in the even summation reactant feed liquid of gained and carries out secondary condensation.
In the present invention, described anil is preferably methylphenylamine, N-ethylaniline, o ethyl aniline and adjacent first
One in base aniline.
In the present invention, the temperature of described secondary condensation is preferably 15～30 DEG C, more preferably 15～20 DEG C；Described secondary contracts
The conjunction response time is preferably 1.5～2.5h, more preferably 2h；Described consecutive condensation pH value is preferably 6.3～7.5, more excellent
Elect 6.5～7 as.In the present invention, rubbing of the compound that there is described in aniline or anil and there is structure shown in Formula IV
You are 1.03～1.5:1 than preferably, more preferably 1.03～1.3:1.
After described secondary condensation, the feed liquid that described secondary condensation is preferably obtained by the present invention carries out successively adsorbing, filters, de-
Salt and concentration, obtain the compound with structure shown in Formula VII.In the present invention, the adsorbent that described absorption uses preferably wraps
Including activated carbon and kieselguhr, concrete can add activated carbon and kieselguhr in the feed liquid that described secondary condensation obtains.At this
In bright, described activated carbon, diatomaceous consumption are preferably and are condensed the 0.5～1.5% of feed liquid quality.The present invention is to described filtration
Method there is no special restriction, use the technical scheme of filtration well known to those skilled in the art, concrete, at this
In bright embodiment, described filtration can use filter pressing bed to carry out, and the filter element specification of described filter pressing bed is preferably PP1.0 μm.
In the present invention, described desalination preferably employs NF membrane and carries out.Described NF membrane molecular weight between 500-1000,
The temperature of heretofore described desalination is preferably 15～35 DEG C, more preferably 20～30 DEG C；The time of described desalination is preferably 3.5
～4.5h, more preferably 4h；PH value during described desalination is preferably 6～7.5, more preferably 6.5～7.
In the present invention, described in be concentrated in the salt that desalination obtains give up electrical conductivity of water less than 0.5ms/cm time, obtain
There is the concentrated solution of Formula VII structural compounds.Described concentration concentration is preferably 13～17%, more preferably 15%.
After obtaining the compound of structure shown in Formula VII, the present invention has the compound of structure shown in Formula VII in acid by described
It is hydrolyzed under the conditions of property, obtains the compound of structure shown in Formulas I.In the present invention, described acid condition is preferably carried by hydrochloric acid
Confession, the present invention is preferably and is added in the concentrated solution with Formula VII structural compounds obtained by hydrochloric acid, and be hydrolyzed reaction.
In the present invention, described hydrolysis temperature is preferably 85～97 DEG C, more preferably 95～97 DEG C；Described hydrolysis time
It is preferably 3.5～4.5h, more preferably 4h；Described hydrolysis pH value is preferably 1～2, more preferably 1～1.5.
After described hydrolysis, the hydrolysis feed liquid obtained is filtered by the present invention successively, desalination, concentration and secondary mistake
Filter, obtains the finished product with Formulas I structure.In the present invention, described filtration is preferably and carries out with the filter element of PP1.0um；
In the present invention, described desalination preferably employs NF membrane and carries out；The pH value of described desalination is preferably 7.5～9, more
It is preferably 8～8.5；The temperature of described desalination is preferably 15～35 DEG C, more preferably 20～30 DEG C；The time of described desalination is preferred
It is 5.5～6.5h, more preferably 6h.
In the present invention, the degree of described concentration is preferably 20～30%, more preferably 25%.
In the present invention, described secondary filter preferably employs nylon filter element and carries out.
Advantageous Effects: compared with existing synthetic method, technical scheme, there is techniques below advantage:
Building-up process is simple；Purity after synthesis is high, eliminates and is conventionally synthesized the step being to saltout, decreases the discharge of waste water；Hydrolysis
With acidic hydrolysis, solve in basic hydrolysis, the problem that by-product is many；The finished product synthesized and conventional synthesis process synthesis
Stable more preferable；Make product more competitive superiority.
Below in conjunction with embodiment, the compound extremely synthetic method of the orchil that the present invention provides is carried out specifically
Bright, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) H-acid dissolves: be distributed in 300g water by 0.1mol H-acid, is then adjusted by the pH of solution with 20% sodium hydroxide
Whole between 6-6.5, after all dissolving, stir 0.5h, standby；
Cyanuric Chloride disperses: by the Cyanuric Chloride of 0.103mol, be distributed in 200g frozen water, disperses 0.5h so that it is dispersion
Uniformly；
Condensation: the H-acid solution that will have dissolved, is slowly added drop-wise in Cyanuric Chloride dispersion liquid, during dropping, does not controls
PH processed, controls temperature 0-5 DEG C, and after dripping, adjusting pH value with sodium bicarbonate powder is 1.8-2.2.Control temperature and pH until
Reaction terminates.TLC (chromatography) detects terminal.
Filter: the condensation solution Medium speed filter paper reacted is filtered, removes the Cyanuric Chloride of excess, in filter process,
Keep temperature 0-5 DEG C.After having filtered, insulation, standby.
(2) diazonium: 0.1mol orthanilic acid, is distributed in 100g water, then adjusts pH with the sodium hydroxide of 20%
Value is to 8 so that it is all dissolve, and stirs 0.5h, then join in solution by 0.103mol sodium nitrite dry powder after dissolving, stirring
To all dissolving, standby.
0.3mol hydrochloric acid is joined in 100g frozen water, stirring, be the most slowly added drop-wise to above-mentioned orthanilic acid and Asia
In nitramine solution, controlling temperature 0-5 DEG C during dropping, after being added dropwise to complete, detection hydrochloric acid and sodium nitrite are the most excessive, keep
Hydrochloric acid and the micro-excess of sodium nitrite, be incubated 0-5 DEG C, is incubated 1h, is subsequently adding 0.5g sulfamic acid, removes the nitrous acid of excess
Sodium, obtains diazol standby.
(3) coupling: diazol is all joined in the condensation substance in the step (1) filtered, then with 15% carbon
Acid sodium adjustment pH value is between 6-6.5, and in coupled processes, temperature controls 5-10 DEG C, after pH value is adjusted, is incubated 2h.
(4) secondary condensation: by the methylphenylamine of 0.103mol, joins in coupling solution, adjusts pH with 15% sodium carbonate
Value is between 7-7.5, and slowly between intensification 15-20 DEG C, and keeps temperature and pH, until reaction terminates, TLC (chromatography) examines
Survey terminal.
Filtration desalination: the feed liquid contracted two, is separately added into the activated carbon into being condensed feed liquid mass fraction 1%, the silicon of 1%
Diatomaceous earth, with pressing depth filtration, deep bed filtration, then with the filter element filtering of PP1.0um, then carries out desalination by NF membrane, has kept liquid level, dyestuff
Concentration is 5%, starts until the electrical conductivity of desalinization wastewater is less than 0.5ms/cm to concentrate, and concentrates concentration to about 15%.
(5) hydrolysis: filter concentrating after desalination in step (4) adding 0.09mol concentration in solution is the hydrochloric acid of 30%,
Adjusting pH value between 1-1.5, be then warmed up to 95 DEG C, insulation, until reaction terminates.TLC (chromatography) detects terminal, then
With 20% sodium hydroxide, pH value is adjusted to 8.
(6) desalination: after the filter element filtering of feed liquid PP1.0um hydrolyzed in step (5), use NF membrane desalination,
It is concentrated to 25% concentration, then obtains finished product after nylon filter element filtering.
Gained finished product 166g, mass concentration is the finished product of 25% concentration, yield 95.6%.(according to real income finished product
Quality and thrown raw material react the mass ratio calculated yield of gained finished product the most completely)
Embodiment 2
(1) H-acid dissolves: be distributed in 300g water by 0.1mol H-acid, is then adjusted by the PH of solution with 20% sodium hydroxide
Whole between 6-6.5, after all dissolving, stir 0.5h, standby；
Cyanuric Chloride disperses: by the Cyanuric Chloride of 0.13mol, be distributed in 200g frozen water, disperses 0.5h so that it is dispersion is all
Even；
Condensation: the H-acid solution that will have dissolved, is slowly added drop-wise in Cyanuric Chloride dispersion liquid, during dropping, does not controls
PH, control temperature 0～5 DEG C, after dripping, adjusting pH value with sodium bicarbonate powder is 1.8～2.2.Control temperature and pH until
Reaction terminates.TLC (chromatography) detects terminal.
Filter: the condensation solution Medium speed filter paper reacted is filtered, removes the Cyanuric Chloride of excess, in filter process,
Keep temperature 0-5 DEG C.After having filtered, insulation, standby.
(2) diazonium: 0.1mol metanilic acid, is distributed in 100g water, then adjusts pH with the sodium hydroxide of 20%
Value is to 8 so that it is all dissolve, and stirs 0.5h, then join in solution by 0.13mol sodium nitrite dry powder after dissolving, stirring
To all dissolving, standby.
0.3mol hydrochloric acid is joined in 100g frozen water, stirring, be the most slowly added drop-wise to above-mentioned metanilic acid and Asia
In nitramine solution, controlling temperature 0～5 DEG C during dropping, after being added dropwise to complete, detection hydrochloric acid and sodium nitrite are the most excessive, protect
Hold hydrochloric acid and the micro-excess of sodium nitrite, be incubated 0～5 DEG C, be incubated 1h, be subsequently adding 0.5g sulfamic acid, remove the nitrous of excess
Acid sodium, obtains diazol standby.
(3) coupling: diazol is all joined in the condensation substance in the step (1) filtered, then with 15% carbon
Acid sodium adjustment pH value is between 6～6.5, and in coupled processes, temperature controls 5～10 DEG C, after pH value is adjusted, is incubated 2h.
(4) secondary condensation: by 0.13mol, o ethyl aniline, joins in coupling solution, adjusts pH with 15% sodium carbonate
Value is between 7～7.5, and slowly heats up between 15～20 DEG C, and keeps temperature and pH, until reaction terminates, and TLC (chromatography)
Detection terminal.
Filtration desalination: the feed liquid contracted two, is separately added into the activated carbon into being condensed feed liquid mass fraction 1%, the silicon of 1%
Diatomaceous earth, with pressing depth filtration, deep bed filtration, then with the filter element filtering of PP1.0um, then carries out desalination by NF membrane, has kept liquid level, dyestuff
Concentration is 5%, starts until the electrical conductivity of desalinization wastewater is less than 0.5ms/cm to concentrate, and concentrates concentration to about 15%.
(5) hydrolysis: filter concentrating after desalination in step (4) adding 0.09mol concentration in solution is the hydrochloric acid of 30%,
Adjustment pH value, between 1～1.5, is then warmed up to 95 DEG C, insulation, until reaction terminates.TLC (chromatography) detects terminal, so
With 20% sodium hydroxide, pH value is adjusted to 8 afterwards.
(6) desalination: after the filter element filtering of feed liquid PP1.0um hydrolyzed in step (5), use NF membrane desalination,
It is concentrated to 25% concentration, then obtains finished product after nylon filter element filtering.
Gained finished product 166g, mass concentration is the finished product of 25% concentration, yield 95.6%.(according to real income finished product
Quality and thrown raw material react the mass ratio calculated yield of gained finished product the most completely)
Embodiment 3
(1) H-acid dissolves: be distributed in 300g water by 0.1mol H-acid, is then adjusted by the pH of solution with 20% sodium hydroxide
Whole between 6-6.5, after all dissolving, stir 0.5h, standby；
Cyanuric Chloride disperses: by the Cyanuric Chloride of 0.15mol, be distributed in 200g frozen water, disperses 0.5h so that it is dispersion is all
Even；
Condensation: the H-acid solution that will have dissolved, is slowly added drop-wise in Cyanuric Chloride dispersion liquid, during dropping, does not controls
PH, control temperature 0～5 DEG C, after dripping, adjusting pH value with sodium bicarbonate powder is 1.8～2.2.Control temperature and pH until
Reaction terminates.TLC (chromatography) detects terminal.
Filter: the condensation solution Medium speed filter paper reacted is filtered, removes the Cyanuric Chloride of excess, in filter process,
Keep temperature 0-5 DEG C.After having filtered, insulation, standby.
(2) diazonium: 0.1mol p-aminobenzene sulfonic acid, is distributed in 100g water, then adjusts pH with the sodium hydroxide of 20%
Value is to 8 so that it is all dissolve, and stirs 0.5h, then join in solution by 0.15mol sodium nitrite dry powder after dissolving, stirring
To all dissolving, standby.
0.3mol hydrochloric acid is joined in 100g frozen water, stirring, be the most slowly added drop-wise to above-mentioned p-aminobenzene sulfonic acid and Asia
In nitramine solution, controlling temperature 0～5 DEG C during dropping, after being added dropwise to complete, detection hydrochloric acid and sodium nitrite are the most excessive, protect
Hold hydrochloric acid and the micro-excess of sodium nitrite, be incubated 0～5 DEG C, be incubated 1h, be subsequently adding 0.5g sulfamic acid, remove the nitrous of excess
Acid sodium, obtains diazol standby.
(3) coupling: diazol is all joined in the condensation substance in the step (1) filtered, then with 15% carbon
Acid sodium adjustment pH value is between 6～6.5, and in coupled processes, temperature controls 5～10 DEG C, after pH value is adjusted, is incubated 2h.
(4) secondary condensation: by the N-ethylaniline of 0.15mol, joins in coupling solution, adjusts pH value with 15% sodium carbonate
Between 7～7.5, and slowly heating up between 15～20 DEG C, and keep temperature and pH, until reaction terminates, TLC (chromatography) examines
Survey terminal.
Filtration desalination: the feed liquid contracted two, is separately added into the activated carbon into being condensed feed liquid mass fraction 1%, the silicon of 1%
Diatomaceous earth, with pressing depth filtration, deep bed filtration, then with the filter element filtering of PP1.0um, then carries out desalination by NF membrane, has kept liquid level, dyestuff
Concentration is 5%, starts until the electrical conductivity of desalinization wastewater is less than 0.5ms/cm to concentrate, and concentrates concentration to about 15%.
(5) hydrolysis: filter concentrating after desalination in step (4) adding 0.09mol concentration in solution is the hydrochloric acid of 30%,
Adjustment pH value, between 1～1.5, is then warmed up to 95 DEG C, insulation, until reaction terminates.TLC (chromatography) detects terminal, so
With 20% sodium hydroxide, pH value is adjusted to 8 afterwards.
(6) desalination: after the filter element filtering of feed liquid PP1.0um hydrolyzed in step (5), use NF membrane desalination,
It is concentrated to 25% concentration, then obtains finished product after nylon filter element filtering.
Gained finished product 166g, mass concentration is the finished product of 25% concentration, yield 95.6%.(according to real income finished product
Quality and thrown raw material react the mass ratio calculated yield of gained finished product the most completely)
Implementation result: be shown in Table shown in 1.2.3.4..
End product embodiment 1-3 obtained mixes with each component of mass ratio in following form, uses successively
The nylon membrane of 0.45 micron and 0.22 micron filters, and obtains being suitable for the ink of inkjet printing.
Table 1
| Composition | Ink A | Ink B | Ink C | Ink D |
| Embodiment 1 end product compound sodium salt | 3 | - | - | - |
| ReactiveRed180 | - | 3 | - | - |
| ReactiveRed141 | - | - | 3 | - |
| ReactiveRed24 | - | - | - | 3 |
| Ultra-pure water | 35 | 35 | 35 | 35 |
| Glycerol | 5 | 5 | 5 | 5 |
| Diethylene glycol | 15 | 15 | 15 | 15 |
| Diethylene glycol monobutyl ether | 5 | 5 | 5 | 5 |
| 1-Methyl-2-Pyrrolidone | 5 | 5 | 5 | 5 |
| Isopropanol | 5 | 5 | 5 | 5 |
Dyestuff in ink A be embodiment 1 end product sodium salt can respectively with embodiment 2 end product of equal quality,
Embodiment 3 end product replaces preparing ink A.
(1) fluency
Test: Epson R 230, print software: photo shop, printing model: high-quality photo prints (image
Enhancement techniques), print paper type: high light printing paper and Alhue paper.
Printing more than page 20 continuously, printing head is tested, and broken string is not for test by fluency.
Ink A, B, C, D are all by printing fluency test.
(2) coloured light:
By the L.A.B value of EYE-ONE test printing color lump, contrasting color distortion, result is as follows:
Table 2
Can be seen that the coloured light that ink A shows on different print media is gold-tinted from test result red, ink
What water B showed on different print media is that blue light is red, and ink C, under different print media, color is also blue light
Redness, ink D and ink A coloured light on different print media is close.
(3) stability test
The most in the following table, 4 weeks later filterability situations of change are observed and with or without heavy with the condition of storage of 60 DEG C and 2 DEG C respectively
Form sediment [each ink filter 150g；PVDF filter paper (aperture 0.45um, diameter 47mm)].It is placed into room temperature to start to filter.
Table 3
Note:
2.pH value situation of change:
Table 4
From test result it can be seen that ink A store under the conditions of 60 DEG C and 2 DEG C 4 weeks still in steady statue, its filterability
Do not change significantly and do not precipitate, and ink B, C, D all have filterability problem in various degree, subject matter to be because activity
Thermal dye stability is bad, and pH is susceptible to change, causes stability to change.
(4) comparison or purity of compound is synthesized
The purity of the compound that embodiment 1.2.3 synthesizes according to technical scheme and the chemical combination of conventional method synthesis
The purity of thing compares: by liquid chromatogram in Figure of description it can be seen that the purity of compound that synthesizes of embodiment 1～3
It is respectively as follows: 97.167%, 98.097%, 97.275%, and the compound of conventional method synthesis only has 95.694%.
As seen from the above embodiment, the dyestuff synthesized by technical scheme is in coloured light, filterability, stability
The dyestuff sold on upper better than market.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. an orchil compound with structure shown in Formulas I:
Wherein R is SO3H, B be: anilino-, methylphenylamine base, N-ethylaniline base, o ethyl aniline base, o-methyl-benzene amido
One.
2. the preparation method of dye composition described in claim 1, comprises the steps:
(1) Cyanuric Chloride and the H-acid with structure shown in Formula II are carried out condensation reaction, obtain the change of structure as shown in formula III
Compound:
(2) compound with structure shown in formula IV is carried out diazo-reaction in an hcl ambient with sodium nitrite, had
Structure diazenium compound shown in Formula V:
(3) what the diazenium compound with Formula V structure described step (2) obtained and described step (1) obtained has formula
The compound of structure shown in III carries out coupling reaction, obtains structural compounds shown in Formula IV:
(4) compound with structure shown in Formula IV that aniline or anil and described step (5) obtain is carried out secondary
Condensation, obtains the compound with structure shown in Formula VII:
(5) shown in the Formula VII described step (4) obtained, the compound of structure is hydrolyzed in acid condition, obtains Formulas I institute
Show the compound of structure；
Not free order between described step (1) and step (2).
3. preparation method as claimed in claim 2, it is characterised in that in described step (1), the temperature of condensation reaction is 0～5
DEG C, the time of condensation reaction is 1～2 hour；Condensation reaction is carried out under conditions of pH value is 5.5～7.
4. preparation method as claimed in claim 2, it is characterised in that the diazo reaction temperature in described seizure (2) is 5～15
DEG C, the diazo reaction time is 0.8～1.2h；Diazo reaction is carried out under conditions of pH value is 6～7.
5. preparation method as claimed in claim 2, it is characterised in that in described step (3), couple temperature is 5～15 DEG C, even
The conjunction time is 0.8～1.2h；Coupling reaction is carried out under conditions of pH value is 6～7.
6. preparation method as claimed in claim 2, it is characterised in that in described step (4), secondary condensation temperature is 15～30
DEG C, the secondary condensation time is 1.5～2.5h；Consecutive condensation is carried out under conditions of pH value is 6.3～7.5.
7. preparation method as claimed in claim 2, it is characterised in that in described step (5), hydrolysis temperature is 85～97 DEG C, water
The solution time is 3.5～4.5h；Hydrolysis is carried out under conditions of pH value is 1～2.
8. preparation method as claimed in claim 2, it is characterised in that in described step (1) Cyanuric Chloride with there is Formula II institute
The mol ratio showing the H-acid of structure is 1.03～1.5:1；
The compound with structure shown in formula IV described in step (2) is 1:1.03～1.5 with the mol ratio of sodium nitrite；
The diazenium compound with Formula V structure described in step (3) and the mol ratio with structural compounds shown in Formula II
For 1:1.03～1.5；
The chemical combination with structure shown in Formula IV that aniline described in step (4) or anil obtain with described step (5)
The mol ratio of thing is 1.03～1.5:1.
9. claim 2 as described in preparation method, it is characterised in that in step (4), anil is methylphenylamine,
N-ethylaniline, o ethyl aniline or o-toluidine.
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