CN102311369A - Preparation method of 1-amino-2-(4-sulfonic acid azobenzene)-8-hydroxy-3,6-disulfonic acid - Google Patents
Preparation method of 1-amino-2-(4-sulfonic acid azobenzene)-8-hydroxy-3,6-disulfonic acid Download PDFInfo
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- CN102311369A CN102311369A CN201110268666A CN201110268666A CN102311369A CN 102311369 A CN102311369 A CN 102311369A CN 201110268666 A CN201110268666 A CN 201110268666A CN 201110268666 A CN201110268666 A CN 201110268666A CN 102311369 A CN102311369 A CN 102311369A
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Abstract
The invention relates to a preparation method of 1-amino-2-(4-sulfonic acid azobenzene)-8-hydroxy-3,6-disulfonic acid. The preparation method adopts sulfanilic acid as an initial raw material and comprises the following steps that sulfanilic acid and hydrochloric acid undergo a reaction to produce a diazonium salt; and the produced diazonium salt and a 1-amino-8-hydroxy-3,6-disulfonic acid solution with a pH value of 7 undergo a reaction in the presence of surfactants of linear fatty amine polyoxyethylene ether and thiourea to produce a final product. Through added linear fatty amine polyoxyethylene ether and thiourea, the reactions are induced to develop towards a desired product generation direction so that good selectivity is realized. Therefore, the preparation method can reduce effectively the generation of a by-product 1-amino-7-(4-sulfonic acid azobenzene)-8-hydroxy-3,6-disulfonic acid, shorten reaction time and improve a desired product yield, wherein the desired product yield is 15% higher than a desired product yield obtained by the prior art.
Description
Technical field
The present invention relates to the field of chemical synthesis, be specifically related to a kind of 1-amino-2-(4-sulfonic acid nitrogen benzide)-8-hydroxyl-3, the preparation technology of 6-disulfonic acid
Background technology
Preparation 1-amino-2-(4-sulfonic acid nitrogen benzide)-8-hydroxyl-3 in the prior art; The technological process of 6-disulfonic acid is: be starting raw material with the Sulphanilic Acid; In the presence of Sodium Nitrite, make it fully to react the formation diazonium salt, the diazonium salt of generation is existed with hydrochloric acid0 ~ 3 ℃, pH=0 ~ 3
Condition under be dissolved into neutral 1-amino-8-hydroxyl-3,6-disulfonic acid solution reaction stops until the diazonium salt reaction of disappearance.Reaction process is seen the formula I:
Ⅰ
< b TranNum=" 94 ">this technological process can produce a large amount of by product 1-amino-7-(4-sulfonic acid nitrogen benzide)-8-hydroxyl-3; 6-disulfonic acid [formula II]; It is 1-amino-2-(4-sulfonic acid nitrogen benzide)-8-hydroxyl-3; The isomer of 6-disulfonic acid, and this by product can't remove through method such as refining, therefore can influence the application performance of title product greatly.</b>
Ⅱ。
Summary of the invention
< b TranNum=" 101 ">technical problem to be solved by this invention is to overcome preparation 1-amino-2-(4-sulfonic acid nitrogen benzide)-8-hydroxyl-3 in the prior art; Can produce the problem of a large amount of by products during the 6-disulfonic acid; A kind of improved 1-amino-2-(4-sulfonic acid nitrogen benzide)-8-hydroxyl-3 is provided; The preparation technology of 6-disulfonic acid reduces the generation of by product, improves the productive rate of title product.</b>
For solving above technical problem, the present invention takes following technical scheme:
A kind of 1-amino-2-(4-sulfonic acid nitrogen benzide)-8-hydroxyl-3, the preparation technology of 6-disulfonic acid comprises following two steps:
(1), make Sulphanilic Acid and hydrochloric acid reaction form diazonium salt;
(2), make the diazonium salt and the 1-amino-8-hydroxyl-3 of step (1) gained, the reaction of 6-disulfonic acid generates 1-amino-2-(4-sulfonic acid nitrogen benzide)-8-hydroxyl-3, the 6-disulfonic acid;
According to the present invention, the detailed process of step (2) is:
After step (1) reaction finishes; Adding straight chain in step (1) the gained diazonium salt reaction solution while stirring is ester fat amine Soxylat A 25-7 and thiocarbamide; In this reaction solution, add 1-amino-8-hydroxyl-3 by the mole equivalent again; The 6-disulfonic acid continues reaction＞4 hours under 3 ~ 30 ℃, the reaction conditions of pH=0.5-1.5, promptly obtain product;
The reacting weight of 0.1mol Sulphanilic Acid wherein, is pressed in < b TranNum=" 115 " >, and straight chain is that the add-on of aliphatic amine polyoxyethylene ether is 0.1 ~ 5g, and the add-on of thiocarbamide is 0.1 ~ 5g.</b>
The reacting weight of 0.1mol Sulphanilic Acid preferably, is pressed in < b TranNum=" 117 " >, and straight chain is that the add-on of aliphatic amine polyoxyethylene ether is 0.1 ~ 2g.</b>
The reacting weight of 0.1mol Sulphanilic Acid preferably, is pressed in < b TranNum=" 119 " >, and the add-on of thiocarbamide is 1 ~ 1.5g.</b>
< b TranNum=" 121 ">preferably, the temperature of reaction of step (2) is 5 ~ 10 ℃.</b>
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
The straight chain that adds among < b TranNum=" 125 ">the present invention is that aliphatic amine polyoxyethylene ether and thiocarbamide can make reaction carry out towards the direction of title product, and the selectivity of reaction is better, thereby can effectively reduce the generation of by product; Preparation technology of the present invention can also shorten the reaction times and improve reaction yield simultaneously, makes the yield of title product be higher than prior art about 15%.</b>
Embodiment
< b TranNum=" 128 ">are done further detailed explanation below in conjunction with concrete embodiment to the present invention, but are not limited to these embodiment.</b>
Embodiment 1
< b TranNum=" 132 ">(1) Sulphanilic Acid 17.32g (0.1mol) in 100g water with among the sodium hydroxide solution 14g and the dissolving; Hydrochloric acid 23g adds water 500g again, ice 100g; Sodium Nitrite 6.9g (0.1mol); Pour in the reactor drum, make said mixture abundant stirring reaction (temperature of reaction is between 0 ~ 12 ℃, and the reaction times is about 2 hours) in reactor drum.</b>
After the reaction of < b TranNum=" 134 ">(2) step (1) finishes; In the gained reaction solution, add the 0.1g thionamic acid to eliminate excessive nitrous acid; Adding straight chain in this reaction solution then is that ester fat amine Soxylat A 25-7 (trade mark AC1810) 1.2g and thiocarbamide 1g fully stir; (this acid forms sodium salt solution with the NaOH neutrality that neutralizes in advance to add 1-amino-8-hydroxyl-3.6-disulfonic acid sodium solution 33.4g again in the reaction solution; The about 0.1mol of molar weight of 1-amino-8-hydroxyl-3.6-disulfonic acid), under pH=0.5-1.5, T=5-10 ℃ reaction conditions, continues reaction 5 hours, promptly get end product.</b>
Embodiment 2
< b TranNum=" 138 ">(1) Sulphanilic Acid 17.32g (0.1mol) in 100g water with among the sodium hydroxide solution 14g and the dissolving; Hydrochloric acid 23g adds water 500g again, ice 100g; Sodium Nitrite 6.9g (0.1mol); Pour in the reactor drum, make said mixture abundant stirring reaction (temperature of reaction is between 0 ~ 12 ℃, and the reaction times is about 2 hours) in reactor drum.</b>
After the reaction of < b TranNum=" 140 ">(2) step (1) finishes; In the gained reaction solution, add the 0.1g thionamic acid to eliminate excessive nitrous acid; Adding straight chain in this reaction solution then is that ester fat amine Soxylat A 25-7 (trade mark AC1810) 2g and thiocarbamide 2.1g fully stir; (this acid forms sodium salt solution with the NaOH neutrality that neutralizes in advance to add 1-amino-8-hydroxyl-3.6-disulfonic acid sodium solution 33.4g again in the reaction solution; The about 0.1mol of molar weight of 1-amino-8-hydroxyl-3.6-disulfonic acid), under pH=0.5-1.5, T=5-10 ℃ reaction conditions, continues reaction 5 hours, promptly get end product.</b>
Comparative Examples 1:
< b TranNum=" 144 ">(1) Sulphanilic Acid 17.32g (0.1mol) in 100g water with among the sodium hydroxide solution 14g and the dissolving; Hydrochloric acid 23g adds water 500g again, ice 100g; Sodium Nitrite 6.9g (0.1mol); Pour in the reactor drum, make said mixture abundant stirring reaction (temperature of reaction is between 0 ~ 12 ℃, and the reaction times is about 2 hours) in reactor drum.</b>
After the reaction of < b TranNum=" 146 ">(2) step (1) finishes; In the gained reaction solution, add the 0.1g thionamic acid to eliminate excessive nitrous acid; (this acid forms sodium salt solution with the NaOH neutrality that neutralizes in advance to add 1-amino-8-hydroxyl-3.6-disulfonic acid sodium solution 33.4g again in the reaction solution; The about 0.1mol of molar weight of 1-amino-8-hydroxyl-3.6-disulfonic acid), under pH=0.5-1.5, T=5-10 ℃ reaction conditions, continues reaction 12 hours, promptly get end product.</b>
Comparative Examples 2:
< b TranNum=" 150 ">(1) Sulphanilic Acid 17.32g (0.1mol) in 100g water with among the sodium hydroxide solution 14g and the dissolving; Hydrochloric acid 23g adds water 500g again, ice 100g; Sodium Nitrite 6.9g (0.1mol); Pour in the reactor drum, make said mixture abundant stirring reaction (temperature of reaction is between 0 ~ 12 ℃, and the reaction times is about 2 hours) in reactor drum.</b>
After the reaction of < b TranNum=" 152 ">(2) step (1) finishes; In the gained reaction solution, add the 0.1g thionamic acid to eliminate excessive nitrous acid; Adding straight chain in this reaction solution then is that ester fat amine Soxylat A 25-7 (trade mark AC1810) 1.2g and urea 1g fully stir; (this acid forms sodium salt solution with the NaOH neutrality that neutralizes in advance to add 1-amino-8-hydroxyl-3.6-disulfonic acid sodium solution 33.4g again in the reaction solution; The about 0.1mol of molar weight of 1-amino-8-hydroxyl-3.6-disulfonic acid), under the reaction conditions of pH=0.5 ~ 1.5, T=5 ~ 10 ℃, continues reaction 5 hours, promptly get end product.</b>
Above each embodiment and Comparative Examples gained end product are analyzed, and the result sees table 1:
Each embodiment of table 1 and Comparative Examples gained end product are analyzed comparing result
⑴ principal product: 1-amino-2-(p-sulfonic acid nitrogen benzide)-8-hydroxyl-3.6-disulfonic acid;
< b TranNum=" 162 ">⑵ by product: 1-amino-7-(p-sulfonic acid nitrogen benzide)-8-hydroxyl-3.6-disulfonic acid.</b>
< b TranNum=" 164 ">can be found out through the comparison of above embodiment and Comparative Examples; Preparation technology of the present invention is better than prior art; Being mainly reflected in the end product yield improves; The purity of title product 1-amino-2-(p-sulfonic acid nitrogen benzide)-8-hydroxyl-3.6-disulfonic acid is higher, and the reaction times shortens, and reaction efficiency is higher.</b>
Among < b TranNum=" 166 ">the present invention; Straight chain is that ester fat amine Soxylat A 25-7 is a kind of interfacial agent; It possibly play the effect of inductor together with thiocarbamide, and the selectivity that reaction is carried out towards the title product direction is better, but they if add excessive; Reaction is worsened, reduce the yield of target compound.</b>
More than the present invention has been done detailed description; Its purpose is to let the personage that is familiar with this art can understand content of the present invention and implements; Can not limit protection scope of the present invention with this; All equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention
Claims (4)
1. a 1-amino-2-(4-sulfonic acid nitrogen benzide)-8-hydroxyl-3, the preparation technology of 6-disulfonic acid comprises following two steps:
(1), make Sulphanilic Acid and hydrochloric acid reaction form diazonium salt;
(2), make the diazonium salt and the 1-amino-8-hydroxyl-3 of step (1) gained, the reaction of 6-disulfonic acid generates 1-amino-2-(4-sulfonic acid nitrogen benzide)-8-hydroxyl-3, the 6-disulfonic acid;
It is characterized in that: the detailed process of step (2) is:
After step (1) reaction finishes; Adding straight chain in step (1) the gained diazonium salt reaction solution while stirring is ester fat amine Soxylat A 25-7 and thiocarbamide; In this reaction solution, add 1-amino-8-hydroxyl-3 by the mole equivalent again; The 6-disulfonic acid continues reaction＞4 hours under 3 ~ 30 ℃, the reaction conditions of pH=0.5-1.5, promptly obtain product;
Wherein, press the reacting weight of 0.1mol Sulphanilic Acid, straight chain is that the add-on of aliphatic amine polyoxyethylene ether is 0.1 ~ 5g, and the add-on of thiocarbamide is 0.1 ~ 5g.
2. preparation technology according to claim 1 is characterized in that: press the reacting weight of 0.1mol Sulphanilic Acid, straight chain is that the add-on of aliphatic amine polyoxyethylene ether is 0.1 ~ 2g.
3. preparation technology according to claim 1 is characterized in that: press the reacting weight of 0.1mol Sulphanilic Acid, the add-on of thiocarbamide is 1 ~ 1.5g.
4. preparation technology according to claim 1 is characterized in that: the temperature of reaction of step (2) is 5 ~ 10 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140690A (en) * | 2014-07-29 | 2014-11-12 | 嘉兴瑞奕环保科技有限公司 | Azo pigment acid coupling reaction auxiliary and application thereof |
| CN108675956A (en) * | 2018-04-12 | 2018-10-19 | 杭州金仕源医药化工有限公司 | A kind of preparation method of nikethamidum |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5787467A (en) * | 1980-11-20 | 1982-05-31 | Nippon Kayaku Co Ltd | Reactive disazo dye |
| CH653671A5 (en) * | 1983-07-06 | 1986-01-15 | Ciba Geigy Ag | METHOD FOR PRODUCING 1-NAPHTHOL-3,6-DISULPHONIC ACID. |
| CN1597789A (en) * | 2004-08-02 | 2005-03-23 | 吴江桃源染料厂 | Preparation technology of azo active dye |
| CN1752150A (en) * | 2005-10-27 | 2006-03-29 | 吴江桃源染料厂 | Preparation technology of azo active dyestuff |
| CN101381527A (en) * | 2007-09-06 | 2009-03-11 | 德州市宇虹化工有限公司 | Method for preparing pigment yellow |
| CN101481540A (en) * | 2008-12-12 | 2009-07-15 | 天津市德凯化工有限公司 | Preparation of reactive blue 2G dye |
| CN101574665A (en) * | 2009-05-25 | 2009-11-11 | 安徽省凤阳染料化工有限公司 | Composite catalyst for coupled reaction of diazo salt and amino-naphthol sulfonic acid substance and application of same |
-
2011
- 2011-09-13 CN CN201110268666A patent/CN102311369A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5787467A (en) * | 1980-11-20 | 1982-05-31 | Nippon Kayaku Co Ltd | Reactive disazo dye |
| CH653671A5 (en) * | 1983-07-06 | 1986-01-15 | Ciba Geigy Ag | METHOD FOR PRODUCING 1-NAPHTHOL-3,6-DISULPHONIC ACID. |
| CN1597789A (en) * | 2004-08-02 | 2005-03-23 | 吴江桃源染料厂 | Preparation technology of azo active dye |
| CN1752150A (en) * | 2005-10-27 | 2006-03-29 | 吴江桃源染料厂 | Preparation technology of azo active dyestuff |
| CN101381527A (en) * | 2007-09-06 | 2009-03-11 | 德州市宇虹化工有限公司 | Method for preparing pigment yellow |
| CN101481540A (en) * | 2008-12-12 | 2009-07-15 | 天津市德凯化工有限公司 | Preparation of reactive blue 2G dye |
| CN101574665A (en) * | 2009-05-25 | 2009-11-11 | 安徽省凤阳染料化工有限公司 | Composite catalyst for coupled reaction of diazo salt and amino-naphthol sulfonic acid substance and application of same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140690A (en) * | 2014-07-29 | 2014-11-12 | 嘉兴瑞奕环保科技有限公司 | Azo pigment acid coupling reaction auxiliary and application thereof |
| CN104140690B (en) * | 2014-07-29 | 2016-06-08 | 嘉兴瑞奕环保科技有限公司 | AZOpigments acid idol reaction promoter and application thereof |
| CN108675956A (en) * | 2018-04-12 | 2018-10-19 | 杭州金仕源医药化工有限公司 | A kind of preparation method of nikethamidum |
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