CN102807527B - Anthrapyridone compounds and its production and use - Google Patents
Anthrapyridone compounds and its production and use Download PDFInfo
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- CN102807527B CN102807527B CN201110145275.0A CN201110145275A CN102807527B CN 102807527 B CN102807527 B CN 102807527B CN 201110145275 A CN201110145275 A CN 201110145275A CN 102807527 B CN102807527 B CN 102807527B
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- 0 *C(C([N+]c1ccc2S)=O)=C(c3ccccc33)c1c2C3=O Chemical compound *C(C([N+]c1ccc2S)=O)=C(c3ccccc33)c1c2C3=O 0.000 description 3
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Abstract
The present invention relates to the method that one prepares structural formula (I) compound or its mixture, in formula (I): a is the integer of 1 ~ 4, R
1be selected from H, OH, CH
3, or C
2h
5, R
2be selected from C
1-6carbalkoxy, COOH or
, M is positively charged ion, is selected from: Li
+, Na
+, K
+,
or N
+(R)
4, wherein R is H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH (CH
3)
2, or CH
2cH
2cH
2cH
3.Described method comprises the steps: that (a) mol ratio is structural formula (II) compound of 1: 1 ~ 3 and m-(beta-hydroxyethyl sulfuryl) aniline of structural formula (III) or p-(beta-hydroxyethyl sulfuryl) aniline compound, in organic solvent, under alkali and copper catalyst exist, ullmann reaction is carried out 2 ~ 6 hours at 110 ~ 140 DEG C, through cooling, reaction product is gone out with elutriation, filter, wash and dry cake, obtain the solid of structural formula (IV) compound, b the solid of the structural formula obtained (IV) compound is added in oleum with such molar ratio by (): in formula (IV) compound and oleum, the mol ratio of sulphur trioxide is 1: 3 ~ 10, sulfonation reaction is carried out at 40-130 DEG C, reaction times is 2-10 hour, after reaction product cool to room temperature, pour in frozen water and make it dilution, with sulfuric acid superfluous in basic salt neutralization reaction system, form throw out, filter and separate throw out, the pH adjusting filtrate is 7-9, remove the inorganic salt impurities in filtrate, obtain saltiness and be no more than structural formula (I) compound of 0.2% or the dye paste of its mixture, drying obtains the pressed powder of structural formula (I) compound or its mixture.The method is simple, cost is low, and the dyestuff made is fast light, resistance to ozone, has water-soluble:
Description
Technical field
The present invention relates to the preparation method of a class Anthrapyridone compounds.
Background technology
In recent years, universal along with computer, ink-jet printer is not only in office but also use more and more general in the family.Ink for spray ink Printing record mainly comprises water color ink and oil-based ink, and in these ink, from the viewpoint of safety, taste, preparation cost, environment protection etc., water color ink is better than oil-based ink.And spray ink Printing, especially the printing of home photos, coloured material in the water color ink use spray ink Printing has higher requirement, first coloured material must be safe, nontoxic, friendly to human and environment, do not affect printing fluency and the blocking shower nozzle of ink, the image that the ink printed be made into goes out and word do not have the diffusion of coloring matter; Secondly, coloured material needs good tone, in water, needs higher solubleness, provides high colour density, and the composition for ink using this coloured material to be made into can steady in a long-termly be preserved, and in preservation process, coloured material does not occur to decompose and deterioration.The more important thing is, this coloured material needs excellent light fastness, to preserve limit more all the year round and few needs that fade to meet people photograph print.In red, yellow, blue or green three primary colors coloured material, compare yellow and cyan coloured material, the problem of the light fastness difference of carmetta coloured material is the most outstanding.JP patent application 89811/1979, JP patent application 143798/1996 and JP patent application 60053/1996 etc. have good tone and distinctiveness containing the magenta dyestuff of xanthene skeleton, but its light fastness is poor.The azoic dyestuff that what patent US6482256B1, US6506241B1 and US20030150354A1 etc. were disclosed is containing H acid, the tone of this kind of azoic dyestuff and water-tolerant, but photostabilization and distinctiveness poor.
Anthrapyridone dyes compound has good tone and boldness as carmetta ink-jet dye, this class formation has description in a lot of patent, dyestuff such as disclosed in JP2000256587A, CN1359411A, CN1507471A, CN1230203A and CN1295600A, but these dyestuffs still do not show gratifying character in light fastness.The light fastness of the magenta dyestuff disclosed in patent WO2009093433A1, US2010075112A1, CN1791643A, CN1795240A and CN101547976A and tone are all very excellent, disclosed in its Patent US2010075112A1, some dyes molecular structure is identical with of the present invention or similar, but its Dyestuff synthesis is complicated, multistep is needed to synthesize, industrialization difficulty is large
Summary of the invention
In order to solve the problems referred to above in this area, the object of this invention is to provide the method for the fast light magenta dyestuff of a kind of synthesis newly, this synthetic method is simple, synthesizes with low cost, easily realizes suitability for industrialized production.
Method of the present invention not only can synthesize the dyestuff as the excellent performance reported in patent US2010075112A1, and the Dyestuff synthesis method of contrast patent US2010075112A1, synthetic method in patent of the present invention is simple, and synthesize with low cost, dyestuff easily realizes suitability for industrialized production.
A first aspect of the present invention relates to the method that one prepares structural formula (I) compound or its mixture, in formula (I):
A is the integer of 1 ~ 4,
R
1be selected from H, OH, CH
3, or C
2h
5,
R
2be selected from C
1-6carbalkoxy, COOH or
M is positively charged ion, is selected from: Li
+, Na
+, K
+,
or N+ (R)
4, wherein R is H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH (CH
3)
2, or CH
2cH
2cH
2cH
3;
Described method comprises the steps:
A () mol ratio is structural formula (II) compound of 1: 1 ~ 3 and m-(beta-hydroxyethyl sulfuryl) aniline of structural formula (III) or p-(beta-hydroxyethyl sulfuryl) aniline compound, in organic solvent, under alkali and copper catalyst exist, ullmann reaction is carried out 2 ~ 6 hours at 110 ~ 140 DEG C, through cooling, go out reaction product with elutriation, filter, wash and dry cake, obtain the solid of structural formula (IV) compound;
B the solid of the structural formula obtained (IV) compound is added in oleum with such molar ratio by (): in formula (IV) compound and oleum, the mol ratio of sulphur trioxide is 1: 3 ~ 10, sulfonation reaction is carried out at 40-130 DEG C, reaction times is 2-10 hour, after reaction product cool to room temperature, pour in frozen water and make it dilution, with sulfuric acid superfluous in basic salt neutralization reaction system, form throw out, filter and separate throw out, the pH adjusting filtrate is 7-9, remove the inorganic salt impurities in filtrate, obtain saltiness and be no more than structural formula (I) compound of 0.2% or the dye paste of its mixture, drying obtains the pressed powder of structural formula (I) compound or its mixture:
In a preferred implementation of aforesaid method, described carbalkoxy is COOCH
3, COOC
2h
5, or COOC
4h
9.
In another preferred embodiment, the organic solvent described in step (a) is DMF or N,N-dimethylacetamide.
In another preferred embodiment, the copper catalyst described in step (a) is Cu (CH
3cOO)
2h
2o or CuSO
4.5H
2o.
In another preferred embodiment, the alkali described in step (a) is selected from following at least one: salt of wormwood, sodium acetate, potassium acetate, imidazoles, sodium hydroxide, potassium hydroxide, sodium carbonate, Quilonum Retard and lithium hydroxide.
In another preferred embodiment, the temperature of the ullmann reaction described in step (a) is 120 DEG C-140 DEG C.
In another preferred embodiment, in the solid of structural formula (IV) compound described in step (b) and oleum, the mol ratio of sulphur trioxide is 1: 4 ~ 8.
In another preferred embodiment, the sulfonation reaction temperature described in step (b) is 80-130 DEG C.
In another preferred embodiment, the basic salt described in step (b) is calcium salt or barium salt.
In another preferred embodiment, described inorganic salt impurities comprise following at least one: sodium salt, lithium salts and calcium salt.
In another preferred embodiment, the inorganic salt impurities removed in filtrate described in step (b) adopts nanofiltration membrane to carry out.
In another preferred embodiment, the drying of the dye paste in step (b) is undertaken by spraying dry.
Accompanying drawing explanation
The preparation process schematic diagram of Fig. 1 formula (I) compound.
Embodiment
In Anthrapyridone dyes compound described in structure above (I) prepared by the present invention:
A is the integer of 1 ~ 4, preferred 2-3;
R
1be selected from H, OH, CH
3, or C
2h
5, be preferably selected from H, CH
3, or C
2h
5, be more preferably selected from H or CH
3;
R
2be selected from C
1-6carbalkoxy, COOH or
preferably
wherein C
1-6the preferred C of carbalkoxy
1-4carbalkoxy, as: COOCH
3, COOC
2h
5, or COOC
4h
9.
M is positively charged ion, is selected from: Li
+, Na
+, K
+,
or N
+(R)
4, wherein R is H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH (CH
3)
2, or CH
2cH
2cH
2cH
3;
M is preferably selected from: Li
+, Na
+, K
+, more preferably Na
+or Li
+;
R is preferably selected from H, CH
3, or CH
2cH
3, more preferably H, CH
3, most preferably H.
Method of the present invention comprises the steps (a) and (b).
Step (a): by the compound of structural formula (II) and m-(beta-hydroxyethyl sulfuryl) aniline or p-(beta-hydroxyethyl sulfuryl) aniline (as shown in formula II I), with the mol ratio of 1: 1 ~ 3, at organic solvent N, dinethylformamide or N, in N-N,N-DIMETHYLACETAMIDE, under alkali and copper catalyst exist, at 110 ~ 140 DEG C, carry out Liv Ullmann (Ullmann) react 2 ~ 6 hours.Through cooling, go out reaction product with elutriation, filter, wash and dry cake, obtain the solid of structural formula (IV) compound:
The synthetic method of the compound of reaction materil structure formula (II) can referenced patent WO2009078252A1, WO2008066062A1, US20100015410A1 and JP2000256587A.
In above-mentioned ullmann reaction of the present invention, the mol ratio of the compound of structural formula (II) and m-(beta-hydroxyethyl sulfuryl) aniline or p-(beta-hydroxyethyl sulfuryl) aniline is preferably 1: 1.2 ~ 1.5.
The organic solvent adopted in ullmann reaction is DMF or N,N-dimethylacetamide, preferred DMF.
Ullmann reaction is temperature required is 110-140 DEG C, preferred 120-140 DEG C, more preferably 130-135 DEG C.
In the method for the invention, the copper catalyst of employing is Cu (CH
3cOO)
2h
2o or CuSO
4.5H
2o, preferred neutralized verdigris, more preferably Cu (CH
3cOO)
2h
2o.
The present invention carries out Liv Ullmann (Ullmann) when reacting, alkali used is not particularly limited, is preferably selected from: at least one in sodium carbonate, salt of wormwood, Quilonum Retard, sodium acetate, potassium acetate, imidazoles, sodium hydroxide, potassium hydroxide and lithium hydroxide etc.More preferably at least one in sodium carbonate, salt of wormwood, Quilonum Retard, sodium hydroxide, potassium hydroxide and lithium hydroxide, more preferred sodium carbonate, Quilonum Retard, sodium hydroxide, most preferably sodium carbonate.
React after 2-6 hour, reaction terminates.Reaction end also can be judged by such supplementary means: the color from yellow of reaction system becomes redness.
Reaction product cooled, preferred cool to room temperature, is poured into water afterwards, evolution reaction product, filters and obtains filter cake, washs (preferably using deionized water) and dry cake, obtains the solid of structural formula (IV) compound.
B the solid of the structural formula obtained (IV) compound is added in oleum with such molar ratio by (): in formula (IV) compound and oleum, the mol ratio of sulphur trioxide is 1: 3 ~ 10, sulfonation reaction is carried out at 40-130 DEG C, reaction times is 2-10 hour, after reaction product cool to room temperature, pour in frozen water and make it dilution, with sulfuric acid superfluous in basic salt neutralization reaction system, form throw out, filter and separate throw out, the pH adjusting filtrate is 7-9, remove the inorganic salt impurities in filtrate, obtain saltiness and be no more than structural formula (I) compound of 0.2% or the dye paste of its mixture, drying obtains the pressed powder of structural formula (I) compound or its mixture:
Wherein in structural formula (IV) compound and oleum, the mol ratio of sulphur trioxide is preferably 1: 4 ~ 8.
Be not particularly limited the concentration of oleum, but preferred concentration is 5-50%, most preferable concentrations is 10-20%.
The temperature of sulfonation reaction is 40 DEG C-130 DEG C, preferred 80-130 DEG C.
After reaction 2-10 hour, reaction terminates, preferred reaction 3-6 hour.
After reaction product cool to room temperature, pour in frozen water and make it dilution, with basic salt, (preferred calcium salt and/or barium salt, as CaO, CaCl
2, Ca (OH)
2, BaCl
2deng) sulfuric acid superfluous in neutralization reaction system, form throw out, filter and isolate throw out.
If the basic salt added is excessive, then need to remove the metal ion introduced owing to introducing basic salt in filtrate, such as calcium and barium ion.Removing mode can adopt one's own profession technique means known in the art.Wherein mode is: the pH adjusting filtrate with alkali is a 9-12, is warming up to 50-80 DEG C, makes the calcium ion in filtrate and/or barium ion and added alkali fully react generation throw out, filter out throw out.PH alkali used is adjusted to comprise and be not limited to: at least one in sodium carbonate, salt of wormwood, Quilonum Retard, sodium hydroxide, potassium hydroxide and lithium hydroxide, preferred sodium carbonate and sodium hydroxide, most preferably sodium carbonate.
Then, preferably use acid (example hydrochloric acid, acetic acid etc.) to adjust the pH of filtrate to be 7-9, and the desalination mode adopting the industry to know, the inorganic salt impurities in removing filtrate.These inorganic salt may come from the inorganic salt introduced due to adjust ph in the impurity inorganic salt or reaction process contained in reaction starting material, such as, as Na salt, lithium salts, calcium salt, NaCl, LiCl etc.
Desalination mode can adopt reverse osmosis membrane mode to carry out.Such as, nanofiltration membrane is adopted.
By desalination, obtain the mill base that saltiness is no more than formula (I) the compound dyestuff of 0.2%, drying, obtains the pressed powder of structural formula (I) compound.
In fact, above-mentionedly obtain the dye paste that saltiness is no more than 0.2% and also without drying, formulate ink can be directly used in.
The mode of described dried dye mill base is preferably spraying dry.
The product prepared can adopt electron spray mass spectrometry to carry out detecting and characterizing.
The method of synthetic dyestuff of the present invention is simple, and synthesize with low cost, dyestuff easily realizes suitability for industrialized production.
Formula (I) the orchil compound synthesized by the inventive method or its mixture can be used as dyestuff, for preparing various ink, ink, coating etc.This dyestuff has good photostabilization, ozone resistance and water-soluble.
In a preferred embodiment, formula (I) compound or its mixture are preferred for the ink for ink-jet print preparing printer.
In a concrete embodiment, ink for ink-jet print (following " % " is mass percent) can be made into according to the following formulation:
The dye composition of structural formula (I) or its mixture: 0.1 ~ 10%
Low-boiling point alcohol: 0 ~ 10%
Wetting Agent for Printing Inks: 2 ~ 30%
Water: 50 ~ 95%
PH value: 6.5 ~ 9.5
Wherein the particular type of low-boiling point alcohol is not particularly limited, one's own profession type known in the art and kind can be adopted, comprise and be not limited to: ethanol, propyl alcohol, Virahol, acetone or methyl alcohol.
Wetting Agent for Printing Inks is high boiling point water-miscible organic solvent, and wetting Agent for Printing Inks particular type is not particularly limited, and can adopt one's own profession type known in the art and kind, comprises and be not limited to: ethylene glycol or its C
1 ~ 5alkyl oxide, propylene glycol or its C
1 ~ 5alkyl oxide, butyleneglycol, pentanediol, hexylene glycol, glycerine, glycol ether or its C
1 ~ 5alkyl oxide, triethylene glycol or its C
1 ~ 5alkyl oxide, TEG or its C
1 ~ 5alkyl oxide, polyoxyethylene glycol, polyvinyl alcohol, dipropylene glycol or its C
1 ~ 5alkyl oxide, tripropylene glycol or its C
1 ~ 5alkyl oxide, 2-Pyrrolidone, N-Methyl pyrrolidone, polyvinylpyrrolidone, polyethylene oxide, poly(propylene oxide) or polyvinyl alcohol etc.
All raw materials (comprising: reaction raw materials formula II compound, formula III compound, oleum, join ink low-boiling point alcohol used and wetting Agent for Printing Inks or high boiling point water-miscible organic solvent etc.) that the present invention adopts all can be commercially available or synthesize by prior art.The synthesis step of dyestuff of the present invention is few, and cost is low, is easy to realize industrialization.
Embodiment
Below, further by embodiment, the present invention is described.In addition, unless otherwise specified, " part " and " % " is herein all quality criteria.λ max refers to dyestuff maximum absorption wavelength in deionized water, the mensuration of the maximum absorption wavelength λ max UV-2540 ultraviolet-visible pectrophotometer that adopts Chinese Shimadzu (Shimadzu) company to produce herein, record maximum absorption wavelength between 480nm ~ 560nm, show have magenta dyestuff of the present invention generate and exist.In this scope, maximum absorption wavelength is comparatively large, shows that the coloured light of orchil is partially blue; Maximum absorption wavelength is less, shows that the coloured light of orchil is partially yellow.
Embodiment 1
(wherein M is Na in the preparation of compound (VI)
+, R
1for CH
3, R
2for
):
(1), under stirring, in 250 parts of DMFs, 50.0 parts of formula (II) compound (R in formula (II) are added
1for CH
3, R
2for
), 45.0 parts of m-(beta-hydroxyethyl sulfuryl) aniline (purity is 90.0%), 13.5 parts of neutralized verdigris monohydrates and 6.0 parts of sodium carbonate, then raised temperature reacts 3 hours at 120 DEG C ~ 130 DEG C.After reaction terminates, be cooled to room temperature, be poured in 300 parts of water, stir 30 minutes, filter, filter cake 300 parts of deionized water wash, filter cake is dried, obtains 63.0 parts, the red solid powder of compound shown in structure formula V.
(2) under the condition of Keep agitation, in the sulfuric acid of 83.0 part 98.0%, slowly add the oleum of 217.0 part 20%, be modulated into the oleum of 300.0 part 12%, toward the pressed powder wherein adding compound shown in 42.8 parts of formulas obtained above (V), raised temperature, carries out the sulfonation reaction of 4 hours in 85 ~ 90 DEG C.After reaction terminates, under agitation reaction solution is slowly poured in 1000 portions of frozen water, slowly add 216.0 parts of calcium hydroxides afterwards, by ice cube holding temperature below 40 DEG C, filter the calcium sulfate of formation and use a small amount of water washing.Filtrate is 11-12 by 30% sodium hydroxide adjust ph, be warmed up to boiling, the throw out that cooled and filtered is formed, regulate filtrate pH to be 7-9 with 10% hydrochloric acid, afterwards by nanofiltration membrane desalination, obtain the dye paste 46 parts containing compound shown in structural formula (VI).
Efficient liquid phase chromatographic analysis shows, and mainly contains a kind of compound in the product dyestuff of synthesis, and electrospray ionization mass spectrum (API-ES) detects, in negative mode, the Theoretical molecular quality of compound is 768.0 (M is in sodium), has mass-to-charge ratio 361.1 (base peak, [M-2Na]
2-/ 2), 723.0 ([M+H-2Na]
-1) all prove that dye molecule molar mass is 768.0, with the theoretical calculation of compound structural formula (VI) Suo Shi.
Shown in structural formula (VI), the maximum absorption wavelength of compound in water is 529.0nm, and the solubleness in water is about 80g/L.
Embodiment 2
(M is Na in the preparation of compound (VII)
+, R
1for CH
3, R
2for
):
Under the condition of Keep agitation, in the sulfuric acid of 83.0 part 98.0%, slowly add the oleum of 217.0 part 20%, be modulated into the oleum of 300.0 part 12%, toward the pressed powder wherein adding above-mentioned formula (V) compound obtained in 42.8 parts of embodiments 1, raised temperature, carries out the sulfonation reaction of 4 hours in 120 ~ 130 DEG C.After sulfonation reaction terminates, then, under agitation reaction solution is slowly poured in 1000 portions of frozen water, slowly add 210.0 parts of calcium hydroxides afterwards, by ice cube holding temperature below 40 DEG C, filter the calcium sulfate of generation and use a small amount of water washing.Filtrate is 11-12 by the sodium hydroxide adjust ph of 30%, be warmed up to boiling, the throw out that cooled and filtered is formed, regulate filtrate pH to be 7-9 with 10% hydrochloric acid, afterwards by nanofiltration membrane desalination, obtain the dye paste 47 parts containing compound shown in structural formula (VII).
Efficient liquid phase chromatographic analysis shows, and mainly contains two peaks in the compound of synthesis, obtains compound VI I-1 (a=2) and compound VI I-2 (a=3) by HPLC preparative separation.In synthetics, the two mass ratio of compound VI I-1 (a=2) and compound VI I-2 (a=3) is 47: 3.
Electrospray ionization mass spectrum (API-ES) detects, and in negative mode, the Theoretical molecular quality of compound VI I-1 is 768.0 (M is in sodium), has mass-to-charge ratio 361.1 (base peak, [M-2Na]
2-/ 2), 723.0 ([M+H-2Na]
-1) all prove that dye molecule molar mass is 768.0, with theoretical calculation.
The Theoretical molecular quality of compound VI I-2 is 870.0 (M is in sodium), has mass-to-charge ratio 267.0 (base peak, [M-3Na]
3-/ 3), 401.0 ([M+H-3Na]
2-/ 2), all prove that dye molecule molar mass is 870.0, with theoretical calculation.
Shown in structural formula (VII), the maximum absorption wavelength of compound in water is 513.5nm, and the solubleness in water is about 120g/L.
Embodiment 3
Adopt the dye composition prepared in embodiment 1-2, with following formulated light red and red ink.
Use EPSONR270 ink-jet printer the light red ink of preparation and red ink to be printed on respectively on Epson glossy photo paper, the image of formation and word are carried out fast light and ozone resistance test.
(A) preparation of ink
The compound water soluble that the present invention obtains is good, use compound obtained in above-described embodiment, according to following formula, light red (LM) and red (M) composition for ink can be prepared respectively, regulate pH=8.0, adding water to cumulative volume is 100ml, filters obtain aqueous ink for inkjet recording composition after stirring with the film filter of 0.22 μm.In addition, in aftermentioned test, use this ink to carry out ink-vapor recording, and evaluate its performance.
Ink screening formulation is as follows:
Comparative example
The present invention selects directly red 227 (as structural formula VIII) of the prior art and reactive red 141 (as structural formula IX) as comparing dyestuff, replace the dye composition of the above-mentioned synthesis of the present invention respectively, other component is identical, prepares water-base ink, carries out printing test.
(B) pattern colour density value (OD value) testing tool and testing method
Colour density test adopts X-Rite instrument.
(C) fast light and ozone resistance test
By different ink printed on Epson glossy photo paper, ultraviolet resistance accelerated test in 83 hours is done under high-intensity ultraviolet light, resistance to ozone test in 1 hour is done under ozone concn is 1 ppm, test the OD value of each sample before and after Acceleration study, adopt below formulae discovery sample at the colour density rate of fall-off OD after t hour
loss%:
OD
Loss％＝(1-OD
t/OD
O)×％
Wherein, OD
tfor elapsed time length is the sample OD value recorded after the test of t hour; OD
ofor the initial OD values that sample is not front after tested, obtain OD value rate of fall-off result as shown in following table (1).
Table (1) is printed fast light, the ozone resistance test result that form image by formulate ink
From table (1) data relatively, ink decided advantage in fast light, ozone resistance that the dyestuff of the inventive method synthesis is prepared.
Claims (6)
1. prepare a method for structural formula (I) compound or its mixture, wherein:
A is the integer of 2-3,
R
1be selected from CH
3, or C
2h
5,
R
2be selected from
M is positively charged ion, is selected from: Li
+, Na
+, K
+;
Described method comprises the steps:
A () mol ratio is structural formula (II) compound of 1:1 ~ 3 and m-(beta-hydroxyethyl sulfuryl) aniline of structural formula (III) or p-(beta-hydroxyethyl sulfuryl) aniline compound, in organic solvent, under alkali and copper catalyst exist, ullmann reaction is carried out 2 ~ 6 hours at 120-140 DEG C, through cooling, go out reaction product with elutriation, filter, wash and dry cake, obtain the solid of structural formula (IV) compound;
B the solid of the structural formula obtained (IV) compound is added in oleum with such molar ratio by (): in formula (IV) compound and oleum, the mol ratio of sulphur trioxide is 1:3 ~ 10, sulfonation reaction is carried out at 80-130 DEG C, reaction times is 2-10 hour, after reaction product cool to room temperature, pour in frozen water and make it dilution, with sulfuric acid superfluous in basic salt neutralization reaction system, form throw out, filter and separate throw out, the pH adjusting filtrate is 7-9, remove the inorganic salt impurities in filtrate, obtain saltiness and be no more than structural formula (I) compound of 0.2% or the dye paste of its mixture, drying obtains the pressed powder of structural formula (I) compound or its mixture:
Organic solvent described in step (a) is DMF or N,N-dimethylacetamide;
Copper catalyst described in step (a) is Cu (CH
3cOO)
2h
2o or CuSO
4.5H
2o;
Alkali described in step (a) is selected from following at least one: salt of wormwood, sodium acetate, potassium acetate, imidazoles, sodium hydroxide, potassium hydroxide, sodium carbonate, Quilonum Retard and lithium hydroxide.
2. the method for claim 1, in the solid of structural formula (IV) compound wherein described in step (b) and oleum, the mol ratio of sulphur trioxide is 1:4 ~ 8.
3. the method for claim 1, the basic salt wherein described in step (b) is calcium salt or barium salt.
4. the method for claim 1, wherein said inorganic salt impurities comprise following at least one: sodium salt, lithium salts and calcium salt.
5. the method for claim 1, the inorganic salt impurities removed in filtrate wherein described in step (b) adopts nanofiltration membrane to carry out.
6. the method for claim 1, the drying of the dye paste wherein in step (b) is undertaken by spraying dry.
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3517013A (en) * | 1964-03-24 | 1970-06-23 | Sumitomo Chemical Co | Anthrapyridone and anthraquinone dyes containing 1 or 2beta-sulfato-,beta-thiosulfato- or beta - vinylethylsulfonylalkanoyl - n - methyleneamine groups |
| US4902798A (en) * | 1986-12-01 | 1990-02-20 | Sumitomo Chemical Co., Ltd. | Anthrapyridone compounds |
| CN1230203A (en) * | 1996-09-11 | 1999-09-29 | 日本化药株式会社 | Anthrapyridone compounds, water-base ink compsn. and articles colored therewith |
| CN1791643A (en) * | 2003-05-22 | 2006-06-21 | 日本化药株式会社 | Novel anthrapyridone compound, aqueous magenta ink composition and inkjet recording method |
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| WO2009078252A1 (en) * | 2007-12-14 | 2009-06-25 | Nippon Kayaku Kabushiki Kaisha | Water-soluble anthrapyridone compound or salt thereof, ink composition, and colored material |
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