CN103030990A - Preparation method of azoic compound - Google Patents
Preparation method of azoic compound Download PDFInfo
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- CN103030990A CN103030990A CN2012102245131A CN201210224513A CN103030990A CN 103030990 A CN103030990 A CN 103030990A CN 2012102245131 A CN2012102245131 A CN 2012102245131A CN 201210224513 A CN201210224513 A CN 201210224513A CN 103030990 A CN103030990 A CN 103030990A
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- 0 *C(C1)=C(C=CC=C2*)C2=C[C@@]1N=Nc(c(*)c1)ccc1N Chemical compound *C(C1)=C(C=CC=C2*)C2=C[C@@]1N=Nc(c(*)c1)ccc1N 0.000 description 1
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Abstract
The invention discloses a preparation method of an azoic compound having the formula A shown in the description to dyes. An azoic dye has high activity, can be color-fixed at a low temperature a in the presence of a small amount of alkaline agent, and is high in fixation rate.
Description
The application is that application number is 201110182915.5, and the applying date is on June 30th, 2011, and denomination of invention is divided an application for the application of " a kind of azo-compound, its preparation method, intermediate and application thereof ".
Technical field
The present invention relates to a kind of azo-compound, its preparation method, intermediate and the application in dyestuff thereof.
Background technology
Reactive dyestuffs are the important synthetic dyestuff of a class, its group by having reactive behavior in the chemical structure and cellulosic fibre generation chemical reaction and therefore set is called again chemically-reactive dyes (Reactive Dyes).Along with the day by day raising of people to sense comfortable and easy to wear and environmental health requirement, textile product is concentrated to cotton and cotton type fabric more and more, and the demand of reactive dyestuffs is also increased sharply year by year, becomes one of present most widely used synthetic dyestuff.
The C.I. reactive yellow 3# that early announces in " Colour Index " (" Colour Index ") is following structure:
C.I. reactive yellow 3#
This dyestuff belongs to the Monozao reactive dyes that contains a chloro-s-triazine active group, is that a bright red light is yellow.Because activity is lower, this dyestuff need comparatively high temps (60 ℃) and higher alkaline agent consumption (20g/L soda ash) are lower can fixation, and degree of fixation is general.
For C.I. reactive yellow 3# structural disadvantages, existing much about its structure is carried out improved report, but up to now, there is no the report of desirable reactive dyestuffs.
Summary of the invention
Technical problem to be solved by this invention is overcome that reactive dyestuffs of the prior art exist active low, fixation severe reaction conditions and the dissatisfactory defective of degree of fixation, and provide a kind of application of azo-compound in dyestuff with double active base, this azoic dyestuff activity is high, can be under lower temperature and less alkaline agent consumption fixation, and have than high colour-fast rate.
Therefore, the present invention relates to a kind of suc as formula the azo-compound shown in the A:
The invention further relates to the preparation method of formula A compound, it comprises the following steps: in the solvent, will and carry out following nucleophilic substitution reaction suc as formula the compound shown in the C suc as formula the compound shown in the B, gets final product;
Wherein, the method for described nucleophilic substitution reaction and condition all can be ordinary method and the condition of this type of reaction of this area.Wherein, described preferred solvents is water.That the volume mass of described solvent and compd B is better is 20 ~ 60ml/g; That better is 40ml/g.That the mol ratio of described compd B and Compound C is better is 1:1.02 ~ 1:1.1; That better is 1:1.05.What the pH of described reaction was better is 5.0 ~ 6.0.What the temperature of described reaction was better is 45 ~ 50 ℃.The time of described reaction is better finish with detection reaction till, be generally 4 ~ 5 hours.
After reaction is finished, described azo-compound A can process by the conventional post-treating method of this compounds of this area, the preferred following post-treating method of the present invention: after the reaction of above-mentioned preparation compd A finishes, the salt (such as sodium-chlor or Repone K) that adds reaction solution volume 5 ~ 25% in the reaction mixture, saltout under stirring, then through press filtration, oven dry, pulverizing and stdn, get final product.
Among the present invention, described compd B can be made by following method: in the solvent, Compound D and compd E are carried out following nucleophilic substitution reaction, get final product;
Wherein, the method for described nucleophilic substitution reaction and condition all can be ordinary method and the condition of this type of reaction of this area.Wherein, described preferred solvents is water.That the volume mass of described solvent and Compound D is better is 20 ~ 60ml/g; That better is 40ml/g.That the mol ratio of described Compound D and compd E is better is 1:1 ~ 1:1.02; That better is 1:1.05.What the pH of described reaction was better is 5.5 ~ 6.5; Better is 6.0.What the temperature of described reaction was better is 0 ~ 10 ℃.The time of described reaction is better finish with detection reaction till, be generally 2 ~ 3 hours.
Among the present invention, described Compound D can be made by following method: compound F 17-hydroxy-corticosterone and compound G are carried out following coupled reaction, get final product;
Wherein, the method for described coupled reaction and condition all can be ordinary method and the condition of this type of reaction of this area, and the present invention is following method and condition particularly preferably: in the water, compound F 17-hydroxy-corticosterone and compound G are reacted, get final product.
That wherein, the volume mass of described water and compound F 17-hydroxy-corticosterone is better is 10 ~ 40ml/g; That better is 30ml/g.That the mol ratio of described compound F 17-hydroxy-corticosterone and compound G is better is 1:1 ~ 1:1.02; That better is 1:1.05.What the pH of described reaction was better is 4.5 ~ 5.0.What the temperature of described reaction was better is 10 ~ 15 ℃.The time of described reaction is better finish with detection reaction till, be generally 1.5 ~ 2.5 hours.
Among the present invention, described compound F 17-hydroxy-corticosterone can be made by following method: compound H is carried out following diazotization reaction, get final product;
Wherein, the method for described diazotization reaction and condition all can be ordinary method and the condition of this type of reaction of this area.
On the basis that meets this area general knowledge, but above-mentioned each preferred feature arbitrary combination among the present invention namely gets the preferred embodiments of the invention.
The invention further relates to suc as formula the application of the azo-compound shown in the A in dyestuff.
Raw material described in the present invention or reagent except specifying, equal commercially available getting.
Positive progressive effect of the present invention is: azo-compound preparation method of the present invention is easy, reaction conditions is gentle, yield is high.This azo-compound be used for dye activity high, can be under lower temperature and less alkaline agent consumption fixation, and have than high colour-fast rate.
Embodiment
The below further specifies the present invention with embodiment, but the present invention is not limited.
Used raw material or reagent is except specifying among the embodiment, all commercially available getting.
Embodiment 1 preparation compd A
Stir lower, in the 250mL there-necked flask, add Amino C Acid 15.2g(0.05mol) and 150g water, with salt acid for adjusting pH to 4.5 ~ 5.0, on the rocksly be cooled to 10 ℃, add 30% hydrochloric acid 15.2g and 35% sodium nitrite solution 10g, temperature remains on 15 ℃, stirs 0.5 hour, adds thionamic acid and consumes excessive Sodium Nitrite.Add 3-acetylaminoaniline 7.9g(0.0525mol), regulate pH to 4.5 ~ 5.0 with soda ash, 5 ℃ of lower stirrings 2 hours, slowly be warming up to 75 ℃, leave standstill, remove upper strata oily matter, add the salt that is equivalent to cumulative volume 25%, stir, suction filtration gets the coupling product filter cake.
In the 250mL beaker, add water 100mL, be warming up to 40 ℃, add above-mentioned filter cake, with pure adjusting PH with base to 6.8 ~ 7.0, make its dissolving, stirred 2 hours, add the gac of cumulative volume 0.5% and 0.5% calcium carbonate, continue to stir 0.5 hour, suction filtration gets the color base filtrate for later use.
In the 100mL there-necked flask, add suitable quantity of water and cyanuric chloride 9.5g(0.0515mol), stirring to pulp.On the rocksly be cooled to 0 ~ 2 ℃, add above-mentioned monoazo color base filtrate, the control temperature is regulated about pH to 6.0 with 10% soda ash liquid below 10 ℃, stirs 2 hours.Add the aqueous solution that is dissolved with 18.4g 5-β-ethyl sulfuryl sulfuric ester-methylphenylamine-4-sulfonic acid, stirred 10 minutes, in 1 hour, be warming up to 45 ℃, regulate pH to 5.0 ~ 6.0, insulation reaction 4 ~ 5 hours with 10% soda ash solution.
After reaction finishes, filtered while hot, filtrate is chilled to 15 ℃, adds by volume 25% sodium-chlor, stirs 1 hour, saltouts, and gets compd A finally by filtration, oven dry, pulverizing, stdn.As calculated, this dyestuff yield is that 90.2%, HPLC detection purity is 74.7%, and its Infrared spectroscopy data are as follows: ~ 3430cm
-1(NH), ~ 2970cm
-1(CH
3), ~ 2930cm
-1(CH
2), ~ 1620cm
-1(carbonyl), ~ 1570cm
-1With ~ 1530cm
-1(aromatic ring and triazine ring), ~ 1410cm
-1(C-H), ~ 1200cm
-1With ~ 1050cm
-1(sulfonic group), ~ 1140cm
-1(ethyl sulfonyl sulfate), ~ 650cm
-1(C-Cl).
Effect embodiment
According to 40 ℃ of dyeings, wherein, the dye level of A is 2%(owf with compd A of the present invention); The alkaline agent consumption is: soda ash 5g/L, caustic soda 1g/L; Dyeing time: 90 minutes.
Reactive yellow K-RN(is C.I. reactive yellow 3#) according to common process dyeing under 60 ℃, the alkaline agent consumption is: soda ash 20g/L; Dyeing time: 60 minutes.
Above-mentioned dyeing course all uses pure cotton knitted fabric to carry out.
Use HunterLab ColorQuestXE Computer color testing instrument that the tinctorial pattern that obtains is carried out strength test, under 2% dye level, the weighed intensities that the weighed intensities that dyestuff of the present invention obtains tinctorial pattern obtains tinctorial pattern than K-RN exceeds that " weighed intensities " is the data that record with above-mentioned color measurement instrument described in nearly 10%(the present invention, it is a relative concept, if compare these data of the two, then be decided to be standard with one of them, namely 100%, another data are the relative value for 100%.In the present embodiment, take the weighed intensities of reactive yellow K-RN as 100%, the compounds of this invention A is 109.83%.), dye utilization rate is greatly improved.Simultaneously, carry out the mensuration of degree of fixation according to the standard of GB/T 2391-2006, the degree of fixation of dyestuff of the present invention can reach 90%, and the degree of fixation of reactive yellow K-RN is 85%.
Claims (1)
1. one kind suc as formula the application of the azo-compound shown in the A in dyestuff,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2012102245131A CN103030990A (en) | 2011-06-30 | 2011-06-30 | Preparation method of azoic compound |
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| CN2012102245131A CN103030990A (en) | 2011-06-30 | 2011-06-30 | Preparation method of azoic compound |
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| CN2011101829155A Division CN102850284A (en) | 2011-06-30 | 2011-06-30 | An azoic compound, and its preparation method, intermediate and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141265A (en) * | 2017-07-03 | 2017-09-08 | 上海安诺其集团股份有限公司 | A kind of azo compound, its preparation method, intermediate and application |
| CN107141264A (en) * | 2017-07-03 | 2017-09-08 | 上海安诺其集团股份有限公司 | A kind of azo compound, its preparation method, intermediate and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0567036B1 (en) * | 1992-04-20 | 1998-07-15 | DyStar Japan Ltd. | Water-soluble monoazodye |
| JP2000290519A (en) * | 1999-04-05 | 2000-10-17 | Sumitomo Chem Co Ltd | Monoazo compound or salt thereof, application to fiber material, and ureide compound or salt thereof |
| JP2001152042A (en) * | 1999-10-05 | 2001-06-05 | Dystar Textilfarben Gmbh & Co Deutschland Kg | Dye mixture of fiber-reactive azo dye and method for dyeing hydroxy group and/or carboxamide group- containing material using the same |
| CN1807517A (en) * | 2006-01-26 | 2006-07-26 | 浙江龙盛集团股份有限公司 | Composite reactive yellow dye |
| CN101597435A (en) * | 2008-06-03 | 2009-12-09 | 上海雅运纺织化工有限公司 | Yellow active dye composition and application thereof |
| CN102108214A (en) * | 2009-12-25 | 2011-06-29 | 上海安诺其纺织化工股份有限公司 | Active yellow dye compound, preparation method thereof and active yellow dye containing active yellow dye component |
-
2011
- 2011-06-30 CN CN2012102245131A patent/CN103030990A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0567036B1 (en) * | 1992-04-20 | 1998-07-15 | DyStar Japan Ltd. | Water-soluble monoazodye |
| JP2000290519A (en) * | 1999-04-05 | 2000-10-17 | Sumitomo Chem Co Ltd | Monoazo compound or salt thereof, application to fiber material, and ureide compound or salt thereof |
| JP2001152042A (en) * | 1999-10-05 | 2001-06-05 | Dystar Textilfarben Gmbh & Co Deutschland Kg | Dye mixture of fiber-reactive azo dye and method for dyeing hydroxy group and/or carboxamide group- containing material using the same |
| CN1807517A (en) * | 2006-01-26 | 2006-07-26 | 浙江龙盛集团股份有限公司 | Composite reactive yellow dye |
| CN101597435A (en) * | 2008-06-03 | 2009-12-09 | 上海雅运纺织化工有限公司 | Yellow active dye composition and application thereof |
| CN102108214A (en) * | 2009-12-25 | 2011-06-29 | 上海安诺其纺织化工股份有限公司 | Active yellow dye compound, preparation method thereof and active yellow dye containing active yellow dye component |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141265A (en) * | 2017-07-03 | 2017-09-08 | 上海安诺其集团股份有限公司 | A kind of azo compound, its preparation method, intermediate and application |
| CN107141264A (en) * | 2017-07-03 | 2017-09-08 | 上海安诺其集团股份有限公司 | A kind of azo compound, its preparation method, intermediate and application |
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Application publication date: 20130410 |