CN100509775C - Preparation method of para-(beta-Ethyl Sulfonyl Sulfate) aniline sulfonic acid - Google Patents
Preparation method of para-(beta-Ethyl Sulfonyl Sulfate) aniline sulfonic acid Download PDFInfo
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- CN100509775C CN100509775C CNB2007101068463A CN200710106846A CN100509775C CN 100509775 C CN100509775 C CN 100509775C CN B2007101068463 A CNB2007101068463 A CN B2007101068463A CN 200710106846 A CN200710106846 A CN 200710106846A CN 100509775 C CN100509775 C CN 100509775C
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- sulfuric ester
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Abstract
The invention is a producing method of a p-(beta-sulfooxyethylsulfone)phenylamine-o-sulfonic acid, which is characterized in that: having the oil of vitriol (100%) as solvent, p-(beta-sulfooxyethylsulfone)phenylamine as material, dispersing at about 60-90 DEG C, sulfonating at 120-130 DEG C, hydrolyze at 100-110 DEG C, then cooling, acidifying, crystallizing, filtering, drying to get product. The active dye produced by p-(beta-sulfooxyethylsulfone)phenylamine-o-sulfonic acid has a better pile-on property, fixing rate, solubility, alkaline saline resistance, humidity resistance, friction fastness compared the dye produced by p-(beta-sulfooxyethylsulfone)phenylamine.
Description
Technical field
The present invention relates to the trichromatic intermediates preparation of dyestuff, particularly a kind of right-preparation method of (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid.
Background technology
As everyone knows, right-(beta-sulfuric ester ethyl sulfonyl) aniline is one of trichromatic important intermediate of preparation reactive dyestuffs, but is still waiting further raising with the performance of its synthetic dyestuff.
Summary of the invention
The purpose of this invention is to provide a kind of right-preparation method of (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, right-(beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid with the inventive method preparation, by its reactive dyestuffs that make than with right-reactive dyestuffs that (beta-sulfuric ester ethyl sulfonyl) aniline makes, its depth, degree of fixation, solubleness, salt tolerant alkaline stability, moisture-proof friction fastness etc. are improved, and easily detergency is better.
The objective of the invention is to realize by following technical scheme.The present invention be a kind of right-preparation method of (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, it is characterized in that may further comprise the steps:
(1) disperse, add the vitriol oil in reactor, under constantly stirring, add right-(beta-sulfuric ester ethyl sulfonyl) aniline, temperature control is at 60-90 ℃, and making beating is uniformly dispersed right-(beta-sulfuric ester ethyl sulfonyl) aniline;
(2) sulfonation, when right-after (beta-sulfuric ester ethyl sulfonyl) aniline is uniformly dispersed, it is warmed up to 120-130 ℃, and under this temperature, reacts, up to unreacted right-(beta-sulfuric ester ethyl sulfonyl) aniline≤0.5% till, obtain the sulfonated bodies of right-(beta-sulfuric ester ethyl sulfonyl) aniline;
(3) hydrolysis, described sulfonated bodies cooled to 58-62 ℃ after, add dilute hydrochloric acid or dilute sulphuric acid, stir, be warmed up to 100-110 ℃, and under this temperature, react, up to the adjacent disulfonic acid of right-(beta-sulfuric ester ethyl sulfonyl) aniline that wherein contains≤till 1.0% o'clock; Obtain work in-process;
(4) make finished product
Continue acidifying after described work in-process are cooled to 8-12 ℃,, after filtration, drying, obtain right-(beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid finished product up to separating out white solid.
The described vitriol oil is 100% sulfuric acid, and described dilute sulphuric acid is 20% sulfuric acid, and described dilute hydrochloric acid is 20% hydrochloric acid.
The described vitriol oil, mol ratio right-(beta-sulfuric ester ethyl sulfonyl) aniline, dilute sulphuric acid are 4.119: 1: 0.381.
The described vitriol oil, mol ratio right-(beta-sulfuric ester ethyl sulfonyl) aniline, dilute hydrochloric acid are 4.119: 1: 0.761.
It is solvent that the present invention adopts the vitriol oil, and right-(beta-sulfuric ester ethyl sulfonyl) aniline is raw material, and dispersion, 120-130 ℃ sulfonation, 100-110 ℃ hydrolysis when temperature is 60-90 ℃ are then through cooling, acidifying, crystallization, filtration, drying and obtain product.When in the conjugated system of dye molecule, add strengthening the polar group of conjugated system electronic effect, can strengthen the polarizing effect of dye molecule, make the mobile enhancing of n electronics, reduce molecule and intensify energy, absorption spectrum is moved to the long wave direction, produce the principle of hyperchromic effect, on the phenyl ring of right-(beta-sulfuric ester ethyl sulfonyl) aniline, introduce sulfonic group, thereby make right-(beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, by its reactive dyestuffs that make with right-reactive dyestuffs that (beta-sulfuric ester ethyl sulfonyl) aniline makes, its depth and performance such as water-soluble are improved, and easily detergency is better.
The yield of goods of the present invention is about 96%, and the product of gained meets desired quality and detects with high-efficient liquid phase chromatogram HPLC, comprises following composition:
Right-(beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid 〉=98%
The adjacent disulfonic acid of right-(beta-sulfuric ester ethyl sulfonyl) aniline≤1.0%
Right-(beta-sulfuric ester ethyl sulfonyl) aniline≤0.25%
Its reaction equation is:
In sum, with intermediate of the present invention right-reactive dyestuffs that (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid makes with existing intermediate right-reactive dyestuffs that (beta-sulfuric ester ethyl sulfonyl) aniline makes, its depth, degree of fixation, solubleness, salt tolerant alkaline stability, moisture-proof friction fastness etc. are improved, and easily detergency is better.
Embodiment
Embodiment 1: with the vitriol oil, right-(beta-sulfuric ester ethyl sulfonyl) aniline add dilute hydrochloric acid prepare intermediate right-(beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, step is as follows:
1. disperse, in reactor, add the 1000kg vitriol oil (100%), under constantly stirring, slowly add 696kg right-(beta-sulfuric ester ethyl sulfonyl) aniline (100%), temperature control 80-85 ℃, pull an oar after 2 hours, check the deployment conditions of right-(beta-sulfuric ester ethyl sulfonyl) aniline, make it not have block the existence;
2. sulfonation, open steam and slowly be warmed up to 125-130 ℃, and under this temperature, reacted 8 hours, high performance liquid chromatography (HPLC) detects, if right-(beta-sulfuric ester ethyl sulfonyl) aniline≤0.5%, then sulfonation puts in place, as right-(beta-sulfuric ester ethyl sulfonyl) aniline〉0.5%, then to continue insulation reaction, till right-(beta-sulfuric ester ethyl sulfonyl) aniline≤0.5%.
3. hydrolysis, after sulfonated bodies is cooled to 60 ℃, add 344kg dilute hydrochloric acid (20%), stir after 1 hour, open steam, slowly be warmed up to 105-110 ℃, and under this temperature, reacted 5 hours, high performance liquid chromatography (HPLC) detects, and as the adjacent disulfonic acid of right-(beta-sulfuric ester ethyl sulfonyl) aniline in the material≤1.0%, then hydrolysis puts in place, as the adjacent disulfonic acid of right-(beta-sulfuric ester ethyl sulfonyl) aniline in the material〉1.0%, then need continue insulation reaction,, obtain work in-process up to the adjacent disulfonic acid of right-(beta-sulfuric ester ethyl sulfonyl) aniline≤1.0%;
4. make product, work in-process are cooled to 10 ℃ after, continue acidifying, up to separating out white solid, after filtration, drying, obtain finished product, yield is about 96%, purity 98.1%.
Embodiment 2: with the vitriol oil, right-(beta-sulfuric ester ethyl sulfonyl) aniline add dilute sulphuric acid prepare intermediate right-(beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, step is as follows:
1. disperse, in reactor, add the 1000kg vitriol oil (100%), under constantly stirring, slowly add 696kg right-(beta-sulfuric ester ethyl sulfonyl) aniline (100%), temperature control 80-85 ℃, pull an oar after 2 hours, check the deployment conditions of right-(beta-sulfuric ester ethyl sulfonyl) aniline, as do not have block the existence, carry out next step;
2. open steam and slowly be warmed up to 125-130 ℃, and reacted 8 hours under this temperature, detect with high performance liquid chromatography (HPLC), as right-(beta-sulfuric ester ethyl sulfonyl) aniline≤0.5%, then sulfonation puts in place; As right-(beta-sulfuric ester ethyl sulfonyl) aniline〉0.5%, then to continue insulation reaction, be qualified up to right-(beta-sulfuric ester ethyl sulfonyl) aniline≤0.5%;
3. after sulfonated bodies being cooled to 60 ℃, add 462kg dilute sulphuric acid (20%), stir after 1 hour, open steam, slowly be warmed up to 105-110 ℃, and reacted 5 hours under this temperature, high performance liquid chromatography (HPLC) detects, as the adjacent disulfonic acid of right-(beta-sulfuric ester ethyl sulfonyl) aniline≤1.0%, then hydrolysis puts in place; As the adjacent disulfonic acid of right-(beta-sulfuric ester ethyl sulfonyl) aniline〉1.0%, then need continue insulation reaction, up to the adjacent disulfonic acid of right-(beta-sulfuric ester ethyl sulfonyl) aniline≤1.0%, obtain work in-process;
4. after subsequently work in-process being cooled to 10 ℃, continue acidifying, up to separating out white solid, after filtration, drying, obtain finished product, yield is about 97%, purity 98.0%.
The effect of goods of the present invention:
The dyestuff that will contain right-(beta-sulfuric ester ethyl sulfonyl) aniline structure as:
With contain the present invention right-dyestuff of (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid structure as:
The detected result of several goods be listed as follows:
As can be seen from the above table, by intermediate of the present invention right-reactive dyestuffs that (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid makes (as black WNN) than with existing intermediate right-reactive dyestuffs (as the C.I. reactive black 5) that (beta-sulfuric ester ethyl sulfonyl) aniline makes, all be significantly increased aspect degree of fixation, solubleness, salt tolerant alkaline stability, enhancing and the moisture-proof friction fastness.
Claims (4)
1. the preparation method of right-(beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid is characterized in that may further comprise the steps:
(1) disperse, add the vitriol oil in reactor, under constantly stirring, add right-(beta-sulfuric ester ethyl sulfonyl) aniline, temperature control is at 60-90 ℃, and making beating is uniformly dispersed right-(beta-sulfuric ester ethyl sulfonyl) aniline;
(2) sulfonation, when right-after (beta-sulfuric ester ethyl sulfonyl) aniline is uniformly dispersed, it is warmed up to 120-130 ℃, and under this temperature, reacts, up to unreacted right-(beta-sulfuric ester ethyl sulfonyl) aniline≤0.5% till, obtain the sulfonated bodies of right-(beta-sulfuric ester ethyl sulfonyl) aniline;
(3) hydrolysis, described sulfonated bodies cooled to 58-62 ℃ after, add dilute hydrochloric acid or dilute sulphuric acid, stir, be warmed up to 100-110 ℃, and under this temperature, react, up to the adjacent disulfonic acid of right-(beta-sulfuric ester ethyl sulfonyl) aniline that wherein contains≤till 1.0% o'clock, obtain work in-process;
(4) make finished product, continue acidifying after described work in-process are cooled to 8-12 ℃,, after filtration, drying, obtain right-(beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid finished product up to separating out white solid.
2. according to claim 1 right-preparation method of (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, it is characterized in that: the described vitriol oil is 100% sulfuric acid, described dilute sulphuric acid is 20% sulfuric acid, described dilute hydrochloric acid is 20% hydrochloric acid.
3. according to claim 2 right-preparation method of (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, it is characterized in that: the described vitriol oil, mol ratio right-(beta-sulfuric ester ethyl sulfonyl) aniline, dilute sulphuric acid are 4.119:1:0.381.
4. according to claim 2 right-preparation method of (beta-sulfuric ester ethyl sulfonyl) aniline ortho-sulfonic acid, it is characterized in that: the described vitriol oil, mol ratio right-(beta-sulfuric ester ethyl sulfonyl) aniline, dilute hydrochloric acid are 4.119:1:0.761.
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| CNB2007101068463A CN100509775C (en) | 2007-05-10 | 2007-05-10 | Preparation method of para-(beta-Ethyl Sulfonyl Sulfate) aniline sulfonic acid |
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| CNB2007101068463A CN100509775C (en) | 2007-05-10 | 2007-05-10 | Preparation method of para-(beta-Ethyl Sulfonyl Sulfate) aniline sulfonic acid |
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| CN100509775C true CN100509775C (en) | 2009-07-08 |
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| CN101633631B (en) * | 2009-08-17 | 2012-10-03 | 浙江劲光化工有限公司 | Method for synthesizing sulfonated para-ester |
| CN102391163A (en) * | 2011-07-04 | 2012-03-28 | 天津德凯化工股份有限公司 | Preparation method of sulfonated para-ester serving as dye intermediate |
| CN102311372A (en) * | 2011-07-04 | 2012-01-11 | 天津德凯化工股份有限公司 | Preparation process of 4-beta-sulfatoethylsulfonyl aniline-2-sulfonic acid |
| CN111393870A (en) * | 2019-01-03 | 2020-07-10 | 上海安诺其集团股份有限公司 | High-salt-alkali-resistance reactive brilliant blue dye and preparation method thereof |
| CN110128306A (en) * | 2019-06-18 | 2019-08-16 | 新乡市锦源化工有限公司 | A kind of preparation method of sulfonated para-ester serving as dye intermediate |
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Non-Patent Citations (4)
| Title |
|---|
| 2-磺酸-4-(β-乙基砜硫酸酯)苯胺的合成研究. 蒋林峰.浙江大学硕士学位论文. 2006 |
| 2-磺酸-4-(β-乙基砜硫酸酯)苯胺的合成研究. 蒋林峰.浙江大学硕士学位论文. 2006 * |
| 染料中间体2-磺酸基-5-β-硫酸酯乙基砜基苯胺的合成. 刘剑等.矿冶，第8卷第1期. 1999 |
| 染料中间体2-磺酸基-5-β-硫酸酯乙基砜基苯胺的合成. 刘剑等.矿冶，第8卷第1期. 1999 * |
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