CN1081697A - Contain azo dispersion dyes of carbazolyl heterocyclic ring and preparation method thereof - Google Patents
Contain azo dispersion dyes of carbazolyl heterocyclic ring and preparation method thereof Download PDFInfo
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- CN1081697A CN1081697A CN 93105523 CN93105523A CN1081697A CN 1081697 A CN1081697 A CN 1081697A CN 93105523 CN93105523 CN 93105523 CN 93105523 A CN93105523 A CN 93105523A CN 1081697 A CN1081697 A CN 1081697A
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- arylamine
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- carbazole
- sulfuric acid
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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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3608—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered heterocyclic ring with only one nitrogen as heteroatom
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Abstract
Contain azo dispersion dyes of carbazolyl heterocyclic ring and preparation method thereof, dye structure such as general formula, Ar is the arylamine parent in the formula, arylamine is 2,5-dichlorphenamide bulk powder, 5-nitro-7-amino-benzene a pair of horses going side by side isothiazole, R is alkyl, hydroxyalkyl, cyano group alkyl or various ester group.The preparation method prepares nitrosyl sulfuric acid earlier, arylamine is added wherein diazotization in 0-65 ℃, adjust in the solution such as adding the coupling component carbazole after the acidity, in 0-60 ℃, carry out coupled reaction, filter, be washed to neutrality, drying then, former dyestuff yield 95%.Dyestuff lovely luster, tinting strength and fastness after commercialization are higher.This law permission temperature of reaction is wide, easy and simple to handle, cost is low.
Description
The present invention relates to a class is azo dispersion dyes of coupling component and preparation method thereof with carbazolyl heterocyclic ring and N-substitutive derivative thereof.
As everyone knows, the coupling component commonly used of preparation azoic dyestuff generally mostly is aromatic amine, phenols and active methylene radical compounds.As coupling component, adopt the synthetic azoic dyestuff of general coupled reaction condition commonly used and method original just difficult with carbazole and N-substitutive derivative thereof, add carbazole and N-alkyl substituent is insoluble in water, more preparation brings difficulty.For addressing these problems, many investigators attempt to be used for quickening coupled reaction by phase-transfer catalyst.But both made under the condition of phase-transfer catalyst, coupled reaction is still carried out not very goodly, and the reaction also need carbazole be dissolved with a large amount of organic solvents such as methylene dichloride, simultaneously the reaction also must carry out at a lower temperature, reaction product very easily becomes the viscosity flow shape, and separating purifies suitable difficulty.
Also there are many investigators to study and carry out coupling with non-phase-transfer catalysis method, as:
The described method of DE-DS2603836, be nitro with cyano group, 2,6 mainly be that different substituent substituted aromatic amines is as diazo component with 4, suspension with carbazole in butanols carries out coupled reaction, adopts this method product separation to purify and has more problem, and productive rate has only 82%.
The method that US3787178 provided, diazo component are thiazole or 2-amido-6-anisole a pair of horses going side by side thiazole.Diazo component is used 90% sulfuric acid dissolution earlier, solution is cooled to-2 ℃ again, adds NaNO again
2The aqueous solution, under the condition that has acetic acid, propionic acid to exist, under 0-50 ℃ of temperature, carry out doazo reaction.Then coupling component N ethyl carbazole is added and wherein carry out coupled reaction, 3-6 ℃ of initial reaction stage temperature, latter temperature 28-30 ℃, reaction times 16-17 hour, products therefrom was molten apart from 5 ℃, no yield report.
The method that DS-OS2338089 provided is: 2,4,5 trichloroaniline diazotization must have HAc to exist, and coupled reaction must have under the dimethyl formamide existence condition and carry out under the lesser temps below 15 ℃, also must regulate with HAc in the reaction.Product separates needs to use methyl alcohol, no yield Fact Sheet.
The method that DE3140716AI provided mainly is suitable for the coupling of adjacent halogen p-Nitroaniline diazonium salt.Diazo component must be earlier with using nitrosyl sulfuric acid diazotization under 20-30 ℃ of temperature behind the acetate dissolution again, then various N-substituted carbazoles are added to and carry out coupled reaction in the diazonium solution, coupling solution acidity about 60%, temperature is no more than 40 ℃, product theoretical yield 98.6%, purity 99.6% but molten apart from bigger.
Main purpose of the present invention is some difficulties that exist when preparing azoic dyestuff with carbazole and N-substitutive derivative thereof as coupling component according to above-mentioned, is intended to design a kind of structural formula and belongs to general structure:
New dye and preparation method thereof.Ar is the parent of the arylamine of benzene series or heterocycle series in the formula, and R is various corresponding alkyl, hydroxyalkyl, cyano group alkyl or various ester group.The temperature of reaction broad that used method allows, operation control is easy, cost is low, yield is high, product separate purify convenient.Bright-coloured, the tinting strength of product color and the fastness of preparation are higher.
The objective of the invention is to realize in the following manner, contain the azo dispersion dyes of carbazolyl heterocyclic ring, its general structure is:
Ar is the parent of arylamine in the formula, and arylamine is 2,5-dichlorphenamide bulk powder, 5-nitro-7-amino-benzene a pair of horses going side by side isothiazole, and R is alkyl, hydroxyalkyl, cyano group alkyl or various ester group.
The preparation method who contains the azo dispersion dyes of carbazolyl heterocyclic ring is earlier with NaNO
2Adding concentration is the dense H more than 70%
2SO
4In, be warming up to 70-85 ℃ again, be incubated 3 minutes, make nitrosyl sulfuric acid.NaNO
2∶H
2SO
4＝3g∶20-40ml。Again with the arylamine of porphyrize room temperature or slightly under the low temperature through the vitriol oil, or behind the vitriol oil-acetate dissolution, directly join in the nitrosyl sulfuric acid, in 0-65 ℃ of scope, carry out diazotization reaction, adjust solution acidity to 40-80%.Diazonium liquid is added in the carbazole of acetate dissolution or N-alkyl carbazole solution carries out coupled reaction.The weight ratio of coupling component and acetic acid is 1: 5-20.0-60 ℃ of coupled reaction temperature, time 5-12 hour.After question response is intact, product is filtered, be washed till neutrality with cold and hot water again after, sneak out journey with general common methods through sand milling, drying, assembly, must the commodity azo dispersion dyes, former dyestuff yield about 95%.
With NaNO
2Adding concentration is the dense H more than 70%
2SO
4In, be warming up to 70-80 ℃ of insulation 3 minutes, make nitrosyl sulfuric acid.NaNO
2∶H
2SO
4＝3g∶35-60ml。Arylamine with porphyrize directly joins in the nitrosyl sulfuric acid again, carries out diazotization reaction in 0-65 ℃ of scope.Thereafter process is same as above.
Contain Ar in the structural formula of azo dispersion dyes of carbazolyl heterocyclic ring and be 2, the 5-dichlorphenamide bulk powder, when R was ethyl, dyestuff was a yellowish-orange crystal powder powder solid, fusing point 141-146 ℃, maximum absorbance is (medium-acetone) about 418mm for λ max.
By the inventive method, need not use alcohols, the organic solvent dissolution carbazole that chloroform etc. are special, arylamine also needn't prior special-purpose acetate dissolution, and can directly add to diazotization in the nitrosyl sulfuric acid, also can use sulfuric acid earlier, or with after the dissolving of sulfuric acid acetic acid mixed solution, add in the nitrosyl sulfuric acid, simplified operation, reduced cost.Diazotization is carried out easy control of reaction system at 0-65 ℃ in than large-temperature range.After diazotization was finished, the acidity of adjusting diazonium liquid with frozen water was to 40-80%, stir certain hour after, add urea and remove unnecessary NaNO
2, again with it in the carbazole compound solution that has slowly joined through acetate dissolution under the room temperature, carry out coupled reaction, though range of reaction temperature is wide to 0-60 ℃, does not have viscosity flow shape product and occur.
Because the acidity of diazonium liquid is to 40-80%, after coupled reaction was intact, filtered coupling raffinate can return use with distillation method Separation and Recovery acid solution, or direct diluent as diazotization liquid, or, be directly used in the preparation of nitrosyl sulfuric acid and the dissolving of fragrant ammonium slightly through concentrating.Filtering product adds the sand milling auxiliary agent and carries out sand milling, obtains the commodity dispersed dye of diffustivity about 4.5 grades.Product color is bright-coloured, tinting strength and fastness are higher, have acidproof preferably, alkaline-resisting, reducing resistance, can be used for hot melt process or high temperature and high pressure method and dye terylene or its BLENDED FABRIC, also can be used for various stamps and dispersion-reduction, dispersion-activity-dyeing of bath method and dye printing.
Below with 3-(2,5-two chloro-nitrogen benzides)-9-ethyl carbazole dyestuff is example explanation preparation method's of the present invention concrete steps:
1, arylamine diazotization:
Place the there-necked flask of cooling bath to add 35ml98%H toward one
2SO
4, under fully stirring, slowly add 2.9gNaNO
2, warming-in-water to 70-80 ℃ transparent to solution, be chilled to room temperature with cooling bath again.At room temperature or 30 ℃ of 6g2,5-dichlorphenamide bulk powder fine powders that stir adding purity＞99% down, continue to stir 30 minutes again, slowly be warming up to 50 ℃ again.Be incubated 1-1.5 hour transparent to material.Diazonium liquid is under agitation slowly poured in the 40g frozen water, continued to stir 10-20 minute, add 0.24g urea, stirred 5 minutes, remove unnecessary NaNO
2, filtering, mother liquor is stand-by.
2, coupled reaction
In there-necked flask, add the 50ml Glacial acetic acid, or the acetic acid of 70-100ml concentration＞50%, add the ethyl carbazole of 6.85g purity 99% wherein after, be warming up to 50-65 ℃ then, be incubated after 2-3 minute, being cooled to room temperature, to get coupling solution stand-by.
Diazonium liquid under room temperature, is added in 20-30 divides clock time in the coupling solution, and reaction is 2 hours about 30 ℃, after about 2 hours, with warming-in-water to 45 ℃ reaction 1 hour, is warming up to 50-60 ℃ of reaction 4-5 hour more again, coupling product.
Product is filtered, wash repeatedly to neutrality with cold water and 90 ℃ of hot water then, refilter oven dry, get 3-(2, the 5-two chloro-nitrogen benzides of yellowish-orange powder crystallization shape)-9-ethyl carbazole product, fusing point 141-146 ℃, maximum absorbance λ max is (medium-acetone) about 418nm.Yield 98%.
3, sand milling
In the tube sand milling jar of the vertical garden of stainless steel, add 2-3mm sand milling granulated glass sphere 150g, MF
49g, oven dry dyestuff 3g, water are an amount of, with 160-500 rev/min speed sand milling 12 hours to diffustivity about 4.5.Take out material, oven dry, promptly making can be for commercial practical azo dispersion dyes.
Adopt preparation method of the present invention, with the step of above-mentioned example or similar step can also be the azo dispersion dyes of coupling component with the carbazolyl heterocyclic ring with what have that the substituent carbazole of different R (seeing attached list) prepares different structure with following different arylamine parent, product has acidproof, alkaline-resisting, anti-reductive performance simultaneously, and has anti-distillation and fast to light characteristics.
Subordinate list
Claims (8)
1, contain the even helium dispersed dye of carbazolyl heterocyclic ring, its general structure is:
Ar is the main body of arylamine in the formula, it is characterized in that arylamine is 2,5-dichlorphenamide bulk powder, 5-nitro-7-amino-benzene a pair of horses going side by side isothiazole, and R is alkyl, hydroxyalkyl, cyano group alkyl or various ester group.
2, dispersed dye according to claim 1, it is characterized in that Ar in the dye structure formula is 2, the 5-dichlorphenamide bulk powder, when R was ethyl, dyestuff was a yellowish-orange crystal powder powder solid, about fusing point 141-146 ℃, maximum absorbance λ max418mm (medium-acetone).
3, the preparation method who contains the azo dispersion dyes of carbazolyl heterocyclic ring is characterized in that earlier NaNO
2Join concentration and be in the vitriol oil more than 70%, when temperature is 70-85 ℃, be incubated 3 minutes then, make nitrosyl sulfuric acid.NaNO
2: H
2SO
4=3g: 20-40ml, again with the arylamine of porphyrize room temperature or slightly under the low temperature through the vitriol oil, or behind the vitriol oil-acetate dissolution, directly join in the nitrosyl sulfuric acid, in 0-65 ℃ of scope, carry out diazotization reaction, adjust solution acidity to 40-80%, diazonium liquid is added in the carbazole of acetate dissolution or N-R base carbazole solution carries out coupled reaction, the weight ratio of coupling component and acetic acid is 1: 5-20,0-60 ℃ of coupled reaction temperature, time 5-12 hour, after question response is intact, product is filtered, after being washed till neutrality with cold and hot water again, with general common methods through sand milling, dry, piece together and sneak out journey, get the commodity azo dispersion dyes, former dyestuff yield about 95%.
4, the preparation method who contains the azo dispersion dyes of carbazolyl heterocyclic ring is characterized in that earlier NaNO
2Add concentration and be in the vitriol oil 70% or more, again temperature is risen to 70-85 ℃ and be incubated 3 minutes, make nitrosyl sulfuric acid, NaNO
2: H
2SO
4=3g: 35-60ml, the arylamine with porphyrize directly joins in the nitrosyl sulfuric acid again, carries out diazotization reaction in 0-65 ℃ of scope, adjusts solution acidity to 40-80%, adds urea behind the stirring certain hour, removes unnecessary NaNO
2Filter, diazonium liquid is added in the carbazole of acetate dissolution or N-R base carbazole solution again and carries out coupled reaction, the weight ratio of coupling component and acetic acid is 1: 5-20,0-60 ℃ of coupled reaction temperature, time 5-12 hour, after question response is intact, product is filtered, after being washed till neutrality with cold and hot water again, sneak out journey with general common methods through sand milling, drying, assembly, get the commodity azo dispersion dyes, its former dyestuff yield about 95%.
5, according to claim 2,3 described methods, the acidity that it is characterized in that adjusting diazonium liquid with frozen water, adds urea and removes unnecessary NaNO behind the stirring certain hour to 40-80%
2, filter, be added to again in the carbazole compound solution.
6,, it is characterized in that the coupling raffinate after product filters can return use with the various acid solutions of distillation method Separation and Recovery according to claim 2,3 described methods.
7,, it is characterized in that the coupling raffinate after product filters can be directly as diazotizing diluent according to claim 2,3 described methods.
8,, it is characterized in that the coupling raffinate after product filters can be directly used in the preparation of nitrosyl sulfuric acid and the dissolving of arylamine slightly through concentrating according to claim 2,3 described methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93105523 CN1081697A (en) | 1993-05-08 | 1993-05-08 | Contain azo dispersion dyes of carbazolyl heterocyclic ring and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93105523 CN1081697A (en) | 1993-05-08 | 1993-05-08 | Contain azo dispersion dyes of carbazolyl heterocyclic ring and preparation method thereof |
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|---|---|
| CN1081697A true CN1081697A (en) | 1994-02-09 |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898857A (en) * | 2012-09-27 | 2013-01-30 | 汤宝祥 | Circulation applying process for mother liquor waste water of coupling reaction |
| CN103086952A (en) * | 2013-02-19 | 2013-05-08 | 连云港珂玫琳科技有限公司 | Preparation method of 4,4'-[(9-butyl-9H-carbazole-3-)methylene]bis[N-methyl-N-phenyl]aniline |
| CN103469403A (en) * | 2013-08-29 | 2013-12-25 | 浙江华孚色纺有限公司 | Novel polyester imitation cotton fiber colored spun yarn and production method thereof |
| CN103497533A (en) * | 2013-09-10 | 2014-01-08 | 江苏亚邦染料股份有限公司 | Heterocyclic azo type disperse dyestuff and application thereof |
-
1993
- 1993-05-08 CN CN 93105523 patent/CN1081697A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898857A (en) * | 2012-09-27 | 2013-01-30 | 汤宝祥 | Circulation applying process for mother liquor waste water of coupling reaction |
| CN103086952A (en) * | 2013-02-19 | 2013-05-08 | 连云港珂玫琳科技有限公司 | Preparation method of 4,4'-[(9-butyl-9H-carbazole-3-)methylene]bis[N-methyl-N-phenyl]aniline |
| CN103086952B (en) * | 2013-02-19 | 2015-05-27 | 连云港珂玫琳科技有限公司 | Preparation method of 4,4'-[(9-butyl-9H-carbazole-3-)methylene]bis[N-methyl-N-phenyl]aniline |
| CN103469403A (en) * | 2013-08-29 | 2013-12-25 | 浙江华孚色纺有限公司 | Novel polyester imitation cotton fiber colored spun yarn and production method thereof |
| CN103469403B (en) * | 2013-08-29 | 2016-03-09 | 浙江华孚色纺有限公司 | A kind of Novel polyester imitation cotton fiber blended color spinning yarn and production method thereof |
| CN103497533A (en) * | 2013-09-10 | 2014-01-08 | 江苏亚邦染料股份有限公司 | Heterocyclic azo type disperse dyestuff and application thereof |
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