CN111592475A - Green preparation method of 1-amino-4-sodium naphthalenesulfonate - Google Patents
Green preparation method of 1-amino-4-sodium naphthalenesulfonate Download PDFInfo
- Publication number
- CN111592475A CN111592475A CN202010455751.8A CN202010455751A CN111592475A CN 111592475 A CN111592475 A CN 111592475A CN 202010455751 A CN202010455751 A CN 202010455751A CN 111592475 A CN111592475 A CN 111592475A
- Authority
- CN
- China
- Prior art keywords
- sodium
- amino
- naphthalenesulfonate
- cooling
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a green preparation method of 1-amino-4-sodium naphthalenesulfonate, relating to the technical field of chemical dye intermediates and comprising the following steps: adding 1-naphthylamine, a surfactant and an organic solvent into a reaction device, heating and stirring, slowly dripping sulfuric acid to generate ammonium sulfate salt when the temperature is raised to 50-70 ℃, wherein the dripping temperature is lower than 85 ℃, and white solid particles are separated out when the dripping is finished within 10-20min after salifying; then heating to 175-190 ℃, performing transposition sulfonation reaction, and continuously performing reflux reaction for 4-8 h; cooling to 100-105 ℃, adding water for dilution, adding sodium carbonate for regulating the pH value of the solution, stirring, cooling to 70-80 ℃, preserving heat, standing for layering, cooling the upper-layer water phase to 15-21 ℃, and crystallizing and filtering to obtain the sodium 1-amino-4-naphthalenesulfonate. The invention uses a liquid phase sulfonation method to improve the synthetic route of the sodium 1,4, reduces the reaction energy barrier and realizes the reaction under the conditions of normal pressure and low temperature.
Description
Technical Field
The invention relates to the technical field of chemical dye intermediates, in particular to a green preparation method of 1-amino-4-sodium naphthalenesulfonate.
Background
Sodium 1-amino-4-naphthalenesulfonate (sodium 1,4 for short) is an important intermediate for synthesizing acidic (direct and active) dye, and can also be used as antidote for nitrite and iodine poisoning. The sodium 1,4 complex can be used for chemoreceptors and absorbers, clinical medical research, and also can be used in the fields of optical devices, thermal switches, optical switches, information storage element materials, DNA structure probes, DNA molecule optical switches, DNA footprint reagents, DNA fragmentation reagents and the like.
Sodium 1,4 (1-amino-4-naphthalene sulfonate) is an important intermediate for medicine, chemical engineering and dye, and its complex can be used in chemoreceptor and absorber and clinical medicine research. Due to the important application, the domestic and international market demand is large at present. However, the existing production process still adopts the traditional baking sulfonation method, and has poor working conditions, high energy consumption and low yield.
Disclosure of Invention
The invention aims to provide a green preparation method of 1-amino-4-sodium naphthalenesulfonate.
In order to achieve the purpose, the invention provides the following technical scheme:
a green preparation method of 1-amino-4-sodium naphthalene sulfonate comprises the following steps: adding 1-naphthylamine, a surfactant and an organic solvent into a reaction device, heating and stirring, slowly dripping sulfuric acid to generate ammonium sulfate salt when the temperature is raised to 50-70 ℃, wherein the dripping temperature is lower than 85 ℃, and white solid particles are separated out when the dripping is finished within 10-20min after salifying; then heating to 175-190 ℃, performing transposition sulfonation reaction, and continuously performing reflux reaction for 4-8 h; cooling to 100-105 ℃, adding water for dilution, adding sodium carbonate for regulating the pH value of the solution, stirring, cooling to 70-80 ℃, preserving heat, standing for layering, cooling the upper-layer water phase to 15-21 ℃, and crystallizing and filtering to obtain the sodium 1-amino-4-naphthalenesulfonate.
Further, the separated lower layer organic adjacent dichlorobenzene is used for sulfonation recycling.
Further, the surfactant is any one of tween 60, tween 80, span 60 and span 80.
Further, the organic solvent is any one of mesitylene, o-dichlorobenzene, ethylene glycol monobutyl ether, 3, 4-dichlorotoluene, nitrobenzene and tetrabromoethane.
Furthermore, a reflux dehydration device is arranged on the reaction device.
Compared with the prior art, the invention has the beneficial effects that: the invention uses a liquid phase sulfonation method to improve the synthetic route of the sodium 1,4, reduces the reaction energy barrier and realizes the reaction under the conditions of normal pressure and low temperature. The surfactant forms a protective layer between the generated product and the reaction device, so that wall built-up materials are reduced, and the generation amount of tar is reduced; on the other hand, the surfactant will enhance the mixing between the solvent and the sulfonic acid, improving the dispersing and suspending ability of the 1-amino-4-naphthalenesulfonic acid.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
adding 35.8g (0.25mol) of 1-naphthylamine, 601.5 g of Tween and 150mL of o-dichlorobenzene into a 500mL reaction bottle with a reflux dehydration device, heating and stirring, raising the temperature to 60 ℃, and slowly dropwise adding sulfuric acid (28 g (0.25mol) w (H) with the mass fraction of 80 percent) into the reaction bottle2SO4) Adding 96% sulfuric acid into 5.6g water to form salt, dropping at 80 deg.c for 10min to separate out white solid particles. Heating to 180 ℃, translocating and sulfonating, and refluxing for 6 h. Cooled to 100 ℃, diluted with 100mL of water and added with 17g of anhydrous Na2CO3Adjusting the pH value to be 8-9, stirring, cooling to 73 ℃, preserving heat, standing and layering, and separating out lower-layer organic adjacent dichlorobenzene for sulfonation recycling; cooling the upper water phase to 20 ℃, crystallizing and filtering to obtain nearly white 1-amino-4-sodium naphthalene sulfonate crystals.
Example 2:
adding 35.8g (0.25mol) of 1-naphthylamine, 601.5 g of Tween and 150mL of o-dichlorobenzene into a 500mL reaction bottle with a reflux dehydration device, heating and stirring, raising the temperature to 50 ℃, and slowly dropwise adding sulfuric acid (28 g (0.25mol) w with the mass fraction of 80%)(H2SO4) Adding 96% sulfuric acid into 5.6g water to form salt, dropping at 80 deg.c for 15min to separate out white solid particles. Heating to 175 ℃, performing transposition sulfonation, and performing reflux reaction for 4 hours. Cooled to 103 ℃, diluted with 100mL of water and added with 17g of anhydrous Na2CO3Adjusting the pH value to be 8-9, stirring, cooling to 70 ℃, preserving heat, standing and layering, and separating out lower-layer organic adjacent dichlorobenzene for sulfonation recycling; cooling the upper water phase to 15 ℃, crystallizing and filtering to obtain nearly white 1-amino-4-sodium naphthalene sulfonate crystals.
Example 3:
adding 35.8g (0.25mol) of 1-naphthylamine, 601.5 g of Tween and 150mL of o-dichlorobenzene into a 500mL reaction bottle with a reflux dehydration device, heating and stirring, raising the temperature to 60 ℃, and slowly dropwise adding sulfuric acid (28 g (0.25mol) w (H) with the mass fraction of 80 percent) into the reaction bottle2SO4) Adding 96% sulfuric acid into 5.6g water to form salt, dropping at 80 deg.c for 20min to separate out white solid particles. Heating to 190 ℃, translocating and sulfonating, and refluxing for 8 h. Cooled to 105 ℃, diluted with 100mL of water and added with 17g of anhydrous Na2CO3Adjusting the pH value to be 8-9, stirring, cooling to 80 ℃, preserving heat, standing and layering, and separating out lower-layer organic adjacent dichlorobenzene for sulfonation recycling; cooling the upper water phase to 21 ℃, crystallizing and filtering to obtain nearly white 1-amino-4-sodium naphthalene sulfonate crystals.
Example 4:
adding 35.8g (0.25mol) of 1-naphthylamine, 801.5 g of Tween and 150mL of mesitylene into a 500mL reaction bottle with a reflux dehydration device, heating and stirring, raising the temperature to 60 ℃, and slowly dropwise adding sulfuric acid (28 g (0.25mol) w (H) with the mass fraction of 80%, (28 g (0.25mol)2SO4) Adding 96% sulfuric acid into 5.6g water to form salt, dropping at 80 deg.c for 10min to separate out white solid particles. Heating to 180 ℃, translocating and sulfonating, and refluxing for 6 h. Cooled to 100 ℃, diluted with 100mL of water and added with 17g of anhydrous Na2CO3Adjusting the pH value to be 8-9, stirring, cooling to 70-80 ℃, preserving heat, standing and layering, and separating out lower-layer organic adjacent dichlorobenzene for sulfonation recycling; on cooling downThe aqueous phase was brought to 20 ℃ and crystallized and filtered to give 69.5g of nearly white crystals of sodium 1-amino-4-naphthalenesulfonate.
Example 5:
adding 35.8g (0.25mol) of 1-naphthylamine, 801.5 g of span and 150mL of ethylene glycol monobutyl ether into a 500mL reaction bottle with a reflux dehydration device, heating and stirring, raising the temperature to 60 ℃, and slowly dropwise adding sulfuric acid (28 g (0.25mol) w (H) with the mass fraction of 80%, (28 g (0.25mol)2SO4) Adding 96% sulfuric acid into 5.6g water to form salt, dropping at 80 deg.c for 10min to separate out white solid particles. Heating to 180 ℃, translocating and sulfonating, and refluxing for 6 h. Cooled to 100 ℃, diluted with 100mL of water and added with 17g of anhydrous Na2CO3Adjusting the pH value to be 8-9, stirring, cooling to 70-80 ℃, preserving heat, standing and layering, and separating out lower-layer organic adjacent dichlorobenzene for sulfonation recycling; cooling the upper water phase to 20 ℃, crystallizing and filtering to obtain nearly white 1-amino-4-sodium naphthalene sulfonate crystals.
Example 6:
35.8g (0.25mol) of 1-naphthylamine, 601.5 g of span and 150mL of 3, 4-dichlorotoluene are added into a 500mL reaction bottle with a reflux dehydration device, the temperature is increased, stirring is carried out, the reaction bottle is heated to 60 ℃, and sulfuric acid with the mass fraction of 80 percent (28 g (0.25mol) w (H) is slowly dropped2SO4) Adding 96% sulfuric acid into 5.6g water to form salt, dropping at 80 deg.c for 10min to separate out white solid particles. Heating to 180 ℃, translocating and sulfonating, and refluxing for 6 h. Cooled to 100 ℃, diluted with 100mL of water and added with 17g of anhydrous Na2CO3Adjusting the pH value to be 8-9, stirring, cooling to 70-80 ℃, preserving heat, standing and layering, and separating out lower-layer organic adjacent dichlorobenzene for sulfonation recycling; cooling the upper water phase to 20 ℃, crystallizing and filtering to obtain nearly white 1-amino-4-sodium naphthalene sulfonate crystals.
The sodium 1,4 is soluble in water but insoluble in ethanol, meanwhile, the 1-naphthylamine is soluble in ethanol but insoluble in water, and tar-like dark residues on the surface of the product are more soluble in ethanol, so that the crude sodium 1,4 is leached and refined by ethanol. The product color is changed into grey white by refining, and the mass fraction is greatly improved. Since only the impurities remained on the surface are washed by the ethanol, the solubility of the sodium 1,4 product in the ethanol is very low, and thus, the yield of the product (the yield in the refining stage in the table) is very low. If water is used for leaching, part of impurities are dissolved by the water, so that the mass fraction of the sodium 1,4 is improved, but the product loss is high during leaching due to the high solubility of the sodium 1,4 in the water, and the yield is greatly reduced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (5)
1. A green preparation method of 1-amino-4-sodium naphthalenesulfonate is characterized by comprising the following steps: the method comprises the following steps: adding 1-naphthylamine, a surfactant and an organic solvent into a reaction device, heating and stirring, slowly dripping sulfuric acid to generate ammonium sulfate salt when the temperature is raised to 50-70 ℃, wherein the dripping temperature is lower than 85 ℃, and white solid particles are separated out when the dripping is finished within 10-20min after salifying; then heating to 175-190 ℃, performing transposition sulfonation reaction, and continuously performing reflux reaction for 4-8 h; cooling to 100-105 ℃, adding water for dilution, adding sodium carbonate for regulating the pH value of the solution, stirring, cooling to 70-80 ℃, preserving heat, standing for layering, cooling the upper-layer water phase to 15-21 ℃, and crystallizing and filtering to obtain the sodium 1-amino-4-naphthalenesulfonate.
2. The green preparation method of sodium 1-amino-4-naphthalenesulfonate according to claim 1, characterized in that: the separated lower layer organic adjacent dichlorobenzene is used for sulfonation recycling.
3. The green preparation method of sodium 1-amino-4-naphthalenesulfonate according to claim 1, characterized in that: the surfactant is any one of tween 60, tween 80, span 60 and span 80.
4. The green preparation method of sodium 1-amino-4-naphthalenesulfonate according to claim 1, characterized in that: the organic solvent is any one of mesitylene, o-dichlorobenzene, ethylene glycol monobutyl ether, 3, 4-dichlorotoluene, nitrobenzene and tetrabromoethane.
5. The green preparation method of sodium 1-amino-4-naphthalenesulfonate according to claim 1, characterized in that: and the reaction device is provided with a reflux dehydration device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010455751.8A CN111592475A (en) | 2020-05-26 | 2020-05-26 | Green preparation method of 1-amino-4-sodium naphthalenesulfonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010455751.8A CN111592475A (en) | 2020-05-26 | 2020-05-26 | Green preparation method of 1-amino-4-sodium naphthalenesulfonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111592475A true CN111592475A (en) | 2020-08-28 |
Family
ID=72188783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010455751.8A Pending CN111592475A (en) | 2020-05-26 | 2020-05-26 | Green preparation method of 1-amino-4-sodium naphthalenesulfonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111592475A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4435336A (en) * | 1981-04-11 | 1984-03-06 | Bayer Aktiengesellschaft | Process for the preparation of aromatic aminosulphonic acids |
| CN110642754A (en) * | 2019-10-10 | 2020-01-03 | 沁阳市季晨化工有限公司 | Preparation process of 1-naphthylamine-4-sodium sulfonate |
-
2020
- 2020-05-26 CN CN202010455751.8A patent/CN111592475A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4435336A (en) * | 1981-04-11 | 1984-03-06 | Bayer Aktiengesellschaft | Process for the preparation of aromatic aminosulphonic acids |
| CN110642754A (en) * | 2019-10-10 | 2020-01-03 | 沁阳市季晨化工有限公司 | Preparation process of 1-naphthylamine-4-sodium sulfonate |
Non-Patent Citations (1)
| Title |
|---|
| 张天永等: ""溶剂法合成1-氨基-4-萘磺酸钠方法的改进"", 《精细化工》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1332940C (en) | Process for preparing 5-sodium sulfo isophthalate | |
| CN102602953B (en) | Method for preparing high borosilicate glass industry-level boric acid by utilizing salt lake lithium-extracting mother solution | |
| CN106565547A (en) | Preparation method of bromaminic acid sodium salt and intermediate of bromaminic acid sodium salt and solvent recovery method | |
| CN104496866A (en) | Continuous sulfonating process for synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulphate | |
| CN107400071A (en) | A kind of bromamine acid production method | |
| CN104193593A (en) | Environment-friendly preparation technology for producing 2-naphthol by liquid phase alkali fusion method | |
| CN104817443A (en) | Benzoin dimethyl ether synthesis process | |
| CN111592475A (en) | Green preparation method of 1-amino-4-sodium naphthalenesulfonate | |
| CN108752202A (en) | Method for preparing trimellitic acid triester by continuous esterification method | |
| CN104016890B (en) | Method for preparing 1-amino-4-sodium naphthalene sulfonate through solid-phase continuous reaction | |
| CN105503628B (en) | A kind of preparation method of D asparatates | |
| CN101139271A (en) | Novel process for producing p-benzoquinone | |
| CN106810412A (en) | A kind of production method of the method and Dispersant MF for improving sulfonating reaction efficiency | |
| CN101182301B (en) | Method for preparing 2-amido-8-naphthol-6-sulfonic acid | |
| CN101367751B (en) | 105% acid sulfonation manufacturing technique of 2-naphthalenol | |
| CN104230764A (en) | Preparation method of 2-acrylamide-2-methyl propanesulfonic acid | |
| CN108003070B (en) | Sulfonation method in H acid production | |
| CN103626695B (en) | New method for preparing fluazinam by using mixed solvent as medium | |
| CN109651070A (en) | A kind of preparation method of 1- naphthalene bromide | |
| CN109422718A (en) | The preparation method of ethyl sulfate | |
| CN101348449B (en) | Preparation of 2,4,5-trichlorobenzene sulfonic acid | |
| CN103242208A (en) | Process for preparing 1, 4-diamino-anthraquinone-2, 3-disulfonic acid by nicotinic acid method | |
| CN102304071A (en) | Method for synthesizing 4.4-dichlorodiphenyl sulfone by two-step process | |
| CN102295591A (en) | Novel preparation method of 4, 4-dichlorodiphenyl sulfone | |
| CN116947269B (en) | Method for recycling chromium and sodium salt from chromium-containing sodium bisulfate wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200828 |
|
| RJ01 | Rejection of invention patent application after publication |