CN111087314A - Synthesis method of 1, 4-diamino anthraquinone and leuco thereof - Google Patents
Synthesis method of 1, 4-diamino anthraquinone and leuco thereof Download PDFInfo
- Publication number
- CN111087314A CN111087314A CN201911325649.XA CN201911325649A CN111087314A CN 111087314 A CN111087314 A CN 111087314A CN 201911325649 A CN201911325649 A CN 201911325649A CN 111087314 A CN111087314 A CN 111087314A
- Authority
- CN
- China
- Prior art keywords
- leuco
- pressure
- sodium hydrosulfite
- improved
- cost
- 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
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 1, 4-diamino anthraquinone and leuco thereof, which comprises the steps of adding 1, 4-dihydroxy anthraquinone, sodium hydroxide, sodium hydrosulfite and ammonia water solution into a high-pressure reaction kettle, sealing the high-pressure kettle, uniformly stirring, heating to 85-95 ℃, carrying out heat preservation reaction for several hours, then cooling to 40-50 ℃, discharging by pressure relief, washing with hot water until the PH is 7-8, and drying to obtain the compound. The sodium hydroxide is added to be matched with the sodium hydrosulfite for use during feeding so as to fully play the reduction function of the sodium hydrosulfite. The product quality is improved, and the cost pressure caused by three-waste treatment is reduced. The purity of the obtained 1, 4-diaminoanthraquinone and leuco thereof is improved from 90% to 95%, the yield is improved from 80% to 88%, the obtained ammonia nitrogen wastewater is halved, and the cost of the ammonia nitrogen wastewater is reduced; the process does not use organic solvent, reduces the using amount of ammonia water, and reduces the cost of recovering and treating the organic solvent.
Description
Technical Field
The invention relates to a method for synthesizing 1, 4-diamino anthraquinone and leuco thereof.
Background
1, 4-diamino anthraquinone is an important fine chemical intermediate, can be used for synthesizing various dyes such as disperse violet 28 and the like, and has pretty high market demand. As the national environmental protection policy is more and more strict, the treatment cost of the high COD organic wastewater and the high ammonia nitrogen wastewater limits the large-scale production of the traditional process, and the purity of the 1, 4-diaminoanthraquinone produced by the traditional process is too low, which is only about 88 percent.
Disclosure of Invention
The invention aims to solve the technical problems of high ammonia nitrogen wastewater and low product purity in the production process of 1, 4-diaminoanthraquinone in the prior art, and provides a synthesis method of 1, 4-diaminoanthraquinone and its leuco body.
In order to solve the technical problems, the invention provides the following technical scheme:
a process for synthesizing 1, 4-diamino anthraquinone and its leuco substance includes such steps as adding 1, 4-dihydroxy anthraquinone, sodium hydroxide, sodium hydrosulfite and ammonia solution to high-pressure reactor, sealing high-pressure reactor, stirring, heating to 85-95 deg.C, holding temp for several hours, cooling to 40-50 deg.C, discharging, washing with hot water until pH is 7-8, and baking.
Further, the pressure in the reaction kettle is 0.3-0.6 MPa.
Further, the mass ratio of the materials is 90% sodium hydrosulfite: 32% sodium hydroxide: 1, 4-dihydroxyanthraquinone leuco: 20% ammonia water (0.8-1.2): (1-1.3):1 (3-5).
The invention has the following beneficial effects: the sodium hydroxide is added to be matched with the sodium hydrosulfite for use during feeding so as to fully play the reduction function of the sodium hydrosulfite. The product quality is improved, and the cost pressure caused by three-waste treatment is reduced. The purity of the obtained 1, 4-diaminoanthraquinone and leuco thereof is improved from 90% to 95%, the yield is improved from 80% to 88%, the obtained ammonia nitrogen wastewater is halved, and the cost of the ammonia nitrogen wastewater is reduced; the process does not use organic solvent, reduces the using amount of ammonia water, and reduces the cost of recovering and treating the organic solvent.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1
A1L autoclave was charged with 90g of 90% sodium hydrosulfite, 116g of 32% sodium hydroxide, 89g of 1, 4-dihydroxyanthraquinone and 215g of 20% aqueous ammonia. The autoclave is closed, the stirring is started, the temperature is raised to 92 ℃ after the stirring is carried out for 30 minutes, the temperature is kept for 4 hours, and the pressure is 0.4 MPa. Cooling to 50 deg.C, relieving pressure, filtering, washing with hot water until the pH of the filtrate is 7-8, and oven drying. 81.4g of the product is obtained, 96 percent of 1, 4-diaminoanthraquinone and leuco thereof are detected by HPLC, and the calculated molar yield is 88 percent.
Example 2
108g of 90% sodium hydrosulfite, 139g of 32% sodium hydroxide, 89g of 1, 4-dihydroxyanthraquinone and 215g of 20% ammonia were charged into a 1L autoclave. The autoclave is closed, the stirring is started, the temperature is raised to 95 ℃ after the stirring is carried out for 30 minutes, the temperature is kept for 4 hours, and the pressure is 0.6 MPa. Cooling to 50 deg.C, relieving pressure, filtering, washing with hot water until the pH of the filtrate is 7-8, and oven drying. 85g of the product is obtained, the total amount of the 1, 4-diaminoanthraquinone and the leuco body thereof is 97 percent through HPLC detection, and the calculated molar yield is 93 percent.
Example 3
A1L autoclave was charged with 81g of 90% sodium hydrosulfite, 105g of 32% sodium hydroxide, 89g of 1, 4-dihydroxyanthraquinone and 215g of 20% aqueous ammonia. The autoclave is closed, the stirring is started, the temperature is raised to 88 ℃ after the stirring is carried out for 30 minutes, the temperature is kept for 4 hours, and the pressure is 0.3 MPa. Cooling to 50 deg.C, relieving pressure, filtering, washing with hot water until the pH of the filtrate is 7-8, and oven drying. 80g of the product is obtained, the total amount of the 1, 4-diaminoanthraquinone and the leuco body thereof is 94 percent through HPLC detection, and the calculated molar yield is 86 percent.
Comparative example 1:
A1L autoclave was charged with 90g of 90% sodium hydrosulfite, 89g of 1, 4-dihydroxyanthraquinone and 430g of 20% aqueous ammonia. The autoclave is closed, the stirring is started, the temperature is raised to 92 ℃ after the stirring is carried out for 30 minutes, the temperature is kept for 4 hours, and the pressure is 0.4 MPa. Cooling to 50 deg.C, relieving pressure, filtering, washing with hot water until the pH of the filtrate is 7-8, and oven drying. 78g of the product is obtained, the total amount of the 1, 4-diamino anthraquinone and the leuco body thereof is 90 percent through HPLC detection, and the calculated molar yield is 80 percent.
Comparative example 2:
A1L autoclave was charged with 90g of 90% sodium hydrosulfite, 89g of 1, 4-dihydroxyanthraquinone and 400g of sulfolane. The autoclave was closed, the stirrer was turned on, and ammonia was introduced to the autoclave to 0.4 MPa. The temperature is raised to 92 ℃ and the temperature is kept for 4 hours. Decompressing, hot filtering to separate waste salt, taking filtrate, cooling to 5-10 ℃, stirring for 1 hour, and filtering. And (5) washing and drying. 60g of the product is obtained, the total amount of the 1, 4-diaminoanthraquinone and the leuco body thereof is 98 percent through HPLC detection, and the calculated molar yield is 67 percent.
Compared with the comparative example 1, the invention reduces the ammonia water dosage by half, and reduces the ammonia nitrogen wastewater treatment cost by half. The purity of the product is improved from 90% to 95%, and the yield is improved from 80% to 88%.
Compared with the comparative example 2, the method cancels the use of organic solvents such as sulfolane, does not generate high COD wastewater, and reduces the cost of recovering the solvents and treating the waste liquid. Meanwhile, the organic solvent can dissolve the product to cause product loss, so that the yield of the process is improved by 21 percent compared with the yield of case 2.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A process for synthesizing 1, 4-diamino anthraquinone and its leuco body includes such steps as adding 1, 4-dihydroxy anthraquinone, sodium hydroxide, sodium hydrosulfite and ammonia solution to high-pressure reactor, sealing high-pressure reactor, stirring, heating to 85-95 deg.C, holding temp for several hours, cooling to 40-50 deg.C, releasing pressure, discharging, washing in hot water until pH is 7-8, and baking.
2. The process for the synthesis of 1, 4-diaminoanthraquinone and its leuco bodies according to claim 1, characterized in that the pressure in the reaction vessel is 0.3-0.6 MPa.
3. The method for synthesizing 1, 4-diaminoanthraquinone and its leuco body according to claim 1, characterized in that the mass ratio of each material is 90% sodium hydrosulfite: 32% sodium hydroxide: 1, 4-dihydroxyanthraquinone leuco: 20% ammonia water (0.8-1.2): (1-1.3):1 (3-5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911325649.XA CN111087314A (en) | 2019-12-20 | 2019-12-20 | Synthesis method of 1, 4-diamino anthraquinone and leuco thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911325649.XA CN111087314A (en) | 2019-12-20 | 2019-12-20 | Synthesis method of 1, 4-diamino anthraquinone and leuco thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111087314A true CN111087314A (en) | 2020-05-01 |
Family
ID=70395228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911325649.XA Pending CN111087314A (en) | 2019-12-20 | 2019-12-20 | Synthesis method of 1, 4-diamino anthraquinone and leuco thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111087314A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082219A (en) * | 2022-08-11 | 2023-05-09 | 山东大学 | Preparation method of disperse blue 60-based disperse dye |
| CN116082176A (en) * | 2022-12-28 | 2023-05-09 | 宁夏建鹏新材料科技有限公司 | Novel synthesis method of 1, 4-diaminoanthraquinone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096120A (en) * | 2018-07-20 | 2018-12-28 | 江苏华尔化工有限公司 | A kind of preparation process of 1,4- diamino anthraquinone leuco compound and oxysome mixture |
-
2019
- 2019-12-20 CN CN201911325649.XA patent/CN111087314A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096120A (en) * | 2018-07-20 | 2018-12-28 | 江苏华尔化工有限公司 | A kind of preparation process of 1,4- diamino anthraquinone leuco compound and oxysome mixture |
Non-Patent Citations (1)
| Title |
|---|
| 沈志平主编: "《染整技术 第2册》", 30 September 2005 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082219A (en) * | 2022-08-11 | 2023-05-09 | 山东大学 | Preparation method of disperse blue 60-based disperse dye |
| CN116082219B (en) * | 2022-08-11 | 2024-04-26 | 山东大学 | Preparation method of disperse blue 60-based disperse dye |
| CN116082176A (en) * | 2022-12-28 | 2023-05-09 | 宁夏建鹏新材料科技有限公司 | Novel synthesis method of 1, 4-diaminoanthraquinone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111087314A (en) | Synthesis method of 1, 4-diamino anthraquinone and leuco thereof | |
| CN108395381B (en) | Synthesis method of 1, 4-diamino anthraquinone leuco body | |
| US2654779A (en) | Method of preparation of guanidino fatty acids | |
| US3654365A (en) | Process for the preparation of para-aminophenol | |
| CN111018747A (en) | Method for refining guanidine nitrate | |
| US4350826A (en) | Process for preparing p-hydroxy phenylglycine | |
| CN111807948B (en) | Preparation method of palladium pivalate | |
| CN108440250B (en) | Process for preparing dihydroxy anthraquinone leuco body | |
| CN109734645B (en) | Synthetic process of isatin | |
| US2351391A (en) | Process for manufacturing 1,3-isoquinolinediols | |
| US2130480A (en) | Process of hydrogenating 5-nitrophthalide | |
| US1714249A (en) | Process of preparing flavanthrone | |
| CN112174910B (en) | Preparation method of hydrogenated flavonol | |
| CN109503561A (en) | A kind of preparation method of thiamine tetrahydrofuryl disfulfide | |
| CN113214088B (en) | Preparation method of 2, 4-dinitroaniline | |
| US1008908A (en) | Vat dyes of the anthraquinone series. | |
| US5424461A (en) | Preparation of 1-amino-4-hydroxyanthraquinone | |
| US4279825A (en) | Process for the preparation of 1,4-diaminoanthraquinone-2,3-disulphonic acid | |
| JPS6122076A (en) | Preparation of fluorene compound | |
| HU185787B (en) | Process for preparing benzoxazolone | |
| CN109503332B (en) | Method for decomposing and recycling sodium phenolate by using salicylic acid residues | |
| US3663539A (en) | Process for the manufacture of basic oxazine dyestuffs | |
| US4435324A (en) | Process for the preparation of 1-alkylaminoanthraquinones | |
| CN108516931B (en) | Preparation method of alpha-ketoleucine calcium | |
| SU469702A1 (en) | Method for preparing 4-nitro-5-aryl-1,2,3-triazole derivatives |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220301 Address after: 213000 room 319, No. 21, Taihu Middle Road, Xinbei District, Changzhou City, Jiangsu Province Applicant after: Changzhou yuepeng Technology Co.,Ltd. Address before: 210000 8 / F, building C, Shilin Industrial Park, No.10 Wanshou Road, Jiangbei new district, Nanjing City, Jiangsu Province Applicant before: NANJING JINHAO MEDICAL TECHNOLOGY Co.,Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200501 |