CN1069896C - Process for preparing 1,4-diamino-2,3-dicyan anthraquinone - Google Patents
Process for preparing 1,4-diamino-2,3-dicyan anthraquinone Download PDFInfo
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- CN1069896C CN1069896C CN97106842A CN97106842A CN1069896C CN 1069896 C CN1069896 C CN 1069896C CN 97106842 A CN97106842 A CN 97106842A CN 97106842 A CN97106842 A CN 97106842A CN 1069896 C CN1069896 C CN 1069896C
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- dicyanoanthraquinone
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- QUZJFTXRXJQLBH-UHFFFAOYSA-N 1,4-diamino-9,10-dioxoanthracene-2,3-dicarbonitrile Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(C#N)C(C#N)=C2N QUZJFTXRXJQLBH-UHFFFAOYSA-N 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000005886 esterification reaction Methods 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 14
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- KZYAYVSWIPZDKL-UHFFFAOYSA-N 1,4-diamino-2,3-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(Cl)C(Cl)=C2N KZYAYVSWIPZDKL-UHFFFAOYSA-N 0.000 claims abstract description 10
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical group [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- PKYGRTHZOTYCAI-UHFFFAOYSA-N tritylazanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C(C=1C=CC=CC=1)([NH3+])C1=CC=CC=C1 PKYGRTHZOTYCAI-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000005273 aeration Methods 0.000 abstract 1
- 150000004056 anthraquinones Chemical class 0.000 abstract 1
- 230000006837 decompression Effects 0.000 abstract 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LYUNBZKEXRUZAO-UHFFFAOYSA-N 1,3-diaminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC(N)=C3C(=O)C2=C1 LYUNBZKEXRUZAO-UHFFFAOYSA-N 0.000 description 2
- WBCXRDHKXHADQF-UHFFFAOYSA-N 4,11-diamino-2-(3-methoxypropyl)naphtho[2,3-f]isoindole-1,3,5,10-tetrone Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(C(N(CCCOC)C1=O)=O)C1=C2N WBCXRDHKXHADQF-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229940001482 sodium sulfite Drugs 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- -1 anthraquinone compounds Chemical class 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011175 product filtration Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a preparation technology of a compound of anthraquinone. In the present invention, 1, 4-diaminoanthraquinone leuco body is used as a principal raw material and the finished product is obtained orderly by the chlorination reaction, the esterification reaction, the sulfonation reaction and the cyanidation reaction. The present invention is characterized in that hydrogen chloride and SO2 generated in the reaction are removed with the method of aeration or decompression after the chlorination reaction, and then, the esterification reaction is directly carried out, wherein the solutions are still organic solvents of chlorbenzene and the proportion by weight of the concentrated sulfuric acid to the 1, 4-diamino-2, 3-dichloroanthraquinone is from 0.5:1 to 1.5:1. The preparation technology has the advantages of short production periodicity, materials and energy sources saving, and few byproducts.
Description
The invention relates to a preparation process of anthraquinone compounds.
1, 4-diamino-2, 3-dicyanoanthraquinone, can be used as a dye intermediate, is an important intermediate for synthesizing bright disperse turquoise blue dye with light resistance, sublimation resistance and excellent fastness performance, such as C.I. disperse blue 60, 99, 143, 175, 176, 198 and the like, and the intermediate is used for synthesizing the currently reported industrial production process of 1, 4-diamino-2, 3-dicyanoanthraquinone, wherein 1, 4-diaminoanthraquinone leuco bodies react with sulfuryl chloride in an inert solvent (such as nitrobenzene and o-dichlorobenzene) to generate 1, 4-diamino-2, 3-dichloroanthraquinone, and then in an excessive concentrated sulfuric acid (the molecular ratio is about 9: 1 and the weight ratio is about 3: 1), esterification is carried out with boric acid, the generated boric acid esterified substance is sulfonated with anhydrous sodium sulfite in an alkaline medium, after sulfonation, thermal filtration is carried out to remove a small amount of insoluble impurities and unreacted 1, 4-diamino-2, 3-dichloroanthraquinone generated 1, 4-diaminoanthraquinone, 3-diaminoanthraquinone, the generated 1, 3-diaminoanthraquinone, 3-dicyanoanthraquinone, is generated, the generated 1, 3-diaminoanthraquinone, 3-dicyanoanthraquinone, is used as an alkaline medium to generate sodium hypochlorite, the alkaline reaction, the alkaline water is not easy to generate a large amount of sodium hypochlorite, and after the esterification reaction, the alkaline water is discharged, the alkaline water is used for drying, the alkaline reaction is used for generating a large amount of sodium hypochlorite, the alkaline sodium hypochlorite is wasted, the alkaline filter cake is not easy to generate a filter cake, the filter cake is not easy to generate a filter cake, the filter cake is generated, the waste is generated, the filter cake is not easy to be used in the filter cake after the filter cake is generated, the filter cake is not easy to.
The invention aims to provide a preparation process of 1, 4-diamino-2, 3-dicyanoanthraquinone, which has short production period, saves materials and energy and has few byproducts.
The technical scheme for realizing the aim of the invention is that the process takes 1, 4-diamino anthraquinone leuco as a main raw material and sequentially carries out chlorination reaction, esterification reaction, sulfonation reaction and cyanidation reaction to obtain a finished product, and is characterized in that after the chlorination reaction, hydrogen chloride gas and sulfur dioxide gas generated by the chlorination reaction are removed by a blast air or reduced pressure method, then the esterification reaction is directly carried out, the used solvent is the chlorobenzene organic solvent used for the chlorination reaction, and the weight ratio of the concentrated sulfuric acid to the 1, 4-diamino-2, 3-dichloro anthraquinone is 0.1: 1-1.5: 1.
In view of the high yield of the product obtained by the process, the water produced by the reaction is distilled off by distillation in the above-mentioned esterification reaction, and the part of the organic solvent lost with the evaporation is added to the system.
In view of making the esterification reaction of the present process more complete and further improving the product yield of the whole process, a quaternary ammonium salt used as a catalyst is also added in the above esterification reaction.
After the sulfonation reaction, the organic solvent is recovered by a blowing and steaming method.
In view of further shortening the reaction period and reducing the energy consumption, the above sulfonation reaction is carried out while recovering the organic solvent by a blowing-steaming method.
In the sulfonation reaction, the weight ratio of concentrated sulfuric acid to 1, 4-diamino-2, 3-dicyanoanthraquinone is 0.6: 1-0.8: 1.
The quaternary ammonium salt is benzyltriethylammonium chloride, dodecyltrimethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide or triphenylmethylammonium chloride, and the weight of the quaternary ammonium salt is 0.01: 1-0.05: 1 compared with that of 1, 4-diamino-2, 3-dichloroanthraquinone.
The chemical equation for each reaction in the above scheme is:
1. chlorination reaction
3. Neutralization reaction
4. Sulfonation reaction
The invention has the positive effects that: (1) after the acid gas generated by chlorination reaction in the process is removed, the rest products and the organic solvent are not required to be separated and are directly subjected to esterification reaction, so that the processes of solvent recovery, product filtration and drying in the original process are omitted. The process is simplified, the period is shortened by 1/3, and the energy consumption is saved. (2) Because the esterification reaction is carried out in an inert organic solvent instead of excessive concentrated sulfuric acid, on one hand, the consumption of sulfuric acid is greatly reduced, further the consumption of alkali during the neutralization reaction is reduced, the generation amount of inorganic salt is greatly reduced, the workload of post-treatment is reduced, the material consumption is reduced, and the energy consumption is further reduced. On the other hand, water generated in the esterification reaction can be removed byadopting distillation or other separation methods, and is not easy to remove in a concentrated sulfuric acid system, so that the esterification reaction is more thorough, and the product yield is improved to a certain extent. (3) The sulfonation reaction can adopt a procedure of blowing and steaming while sulfonating, so that the process is simplified, the time is shortened, and the energy is saved, the total yield of the process is 87-90%, the process is improved by 3-9% compared with 81-84% of the prior process, and the purity of the product obtained by the process can reach 93.5-94%, and is slightly improved by 92-93% compared with the prior process.
The present invention is further described below with reference to examples.
In the case of the example 1, the following examples are given,
24 g of powdery 1, 4-diaminoanthraquinone leuco body is added into a four-neck flask containing 130 g of o-dichlorobenzene liquid, and 50 g of sulfuryl chloride liquid is slowly dropped at the temperature of 20-40 ℃ so as to control the chlorination reaction speed for 2-4 hours. After dripping, heating to 50-60 ℃, and continuing to perform heat preservation reaction for 4-6 hours until the reaction is complete. Then, the acidic gases of hydrogen chloride and sulfur dioxide and the residual sulfuryl chloride generated by the reaction are removed by blowing or reducing pressure and absorbed by alkali liquor. 13 g of boric acid, 20 g of 100% concentrated sulfuric acid and 0.5 g of benzyltriethylammonium chloride as quaternary ammonium salt are added into a four-neck flask, the temperature is raised to 110-130 ℃, water generated in the reaction and part of o-dichlorobenzene are distilled under reduced pressure while the reaction is carried out, and the o-dichlorobenzene lost in the reduced pressure distillation is replenished at any time until the reaction is completed. The whole esterification reaction takes about 6 to 8 hours. And then, cooling the system to 0-20 ℃, performing neutralization reaction by using about 40 g of 40% sodium hydroxide, and adjusting the pH value of the system to 8-11. And (3) adding 26 g of sodium sulfite during the sulfonation reaction, heating to 90-100 ℃, performing the sulfonation reaction and recovering the o-dichlorobenzene by blowing and steaming at the same time until the reaction is complete and the solvent is recovered for about 3-4 hours, wherein the obtained sulfonate is in a dissolved state. After recovery, the mixture is filtered while hot, the filter residue is a small amount of unreacted solid 1, 4-diamino-2, 3-dichloroanthraquinone and other impurities, and the filter residue is washed by hot water. And collecting the filtrate and all washing liquor, putting the filtrate and all washing liquor into a clean three-neck flask, adjusting the pH value to 7-10, adding 10 g of sodium cyanide to perform a cyanidation reaction, heating to 80-100 ℃, and keeping the temperature for reaction for 4-6 hours until the reaction is complete, so that the obtained product is separated out. Then adding 10 g of sodium bicarbonate to decompose residual sodium cyanide, and stirring for 0.5-1 hour until the decomposition reaction is complete. After the decomposition reaction, the reaction mixture was filtered, washed with water and dried to obtain 27 g of 1, 4-diamino-2, 3-dicyanoanthraquinone, the total yield was 88%, and the purity was 94%.
And after the cyanide waste liquid and the concentrated washing liquid after the decomposition reaction are recovered, dilute sulfuric acid or dilute hydrochloric acid is added for acidification to separate out colored solids, and the colored solids are filtered. The waste residue is used as solid waste and can be treated by a burying method or sent to a waste treatment plant for unified treatment. The acidic filtrate is further neutralized with lime, filtered and discharged.
The chemical equation for the NaCN decomposition reaction is as follows:
in the case of the example 2, the following examples are given,
24 g of 1, 4-diaminoanthraquinone leuco compound is added into 150 g of chlorobenzene, and 55 g of sulfuryl chloride is dropwise added at 20-40 ℃ for 2-3 hours. After dripping, reacting for 3-5 hours at 40-60 ℃, and then removing and absorbing residual sulfuryl chloride and hydrogen chloride and sulfur dioxide gas generated by reaction in the system by using alkali liquor. Adding 15 g of boric acid, 1 g of benzyltriethylammonium chloride and 22 g of 98% sulfuric acid, heating to 110-140 ℃, refluxing partial chlorobenzene while reacting, removing water in the chlorobenzene, and supplementing the chlorobenzene which is a solvent lost by reduced pressure distillation at any time until the reaction is finished, wherein the time is about 6-10 hours. And then, cooling the system to 0-20 ℃, adjusting the pH value of the system to 8-11 by using liquid caustic soda, adding 28 g of sodium sulfite, heating to 90-100 ℃, and performing sulfonation reaction while recovering the solvent by blowing and steaming. Until the recovery is completed. Filtering while the solution is hot, removing unreacted 1, 4-diamino-2, 3-dichloroanthraquinone and other impurities, and collecting filtrate and all washing liquor for cyanidation. Adjusting the pH value to 7-11 by using concentrated alkali, adding 10 g of sodium cyanide, and carrying out heat preservation reaction at 80-100 ℃ for 4-6 hours. Then 10 g of sodium bicarbonate is added to decompose the unreacted sodium cyanide, and after stirring for 1 hour, the mixture is filtered, washed and dried to obtain 28 g of 1, 4-diamino-2, 3-dicyanoanthraquinone, wherein the total yield is 90 percent, and the product purity is 94 percent.
In the case of the example 3, the following examples are given,
the remainder of the process was the same as in example 1, except that dodecyltrimethylammonium chloride was used as the quaternary ammonium salt in an amount of 1.5 g.
In the case of the example 4, the following examples are given,
the remainder of the procedure was the same as in example 1, except that benzyltrimethylammonium chloride was used as the quaternary ammonium salt in an amount of 1 g.
In the case of the example 5, the following examples were conducted,
the remainder of the process was the same as in example 1, except that tetrabutylammonium bromide was used in an amount of 0.7 g.
In the case of the example 6, it is shown,
the remainder of the process was the same as in example 1 except that 0.6 g of triphenylmethylammonium chloride was used as the quaternary ammonium salt.
Claims (7)
1. A preparation process of 1, 4-diamino-2, 3-dicyanoanthraquinone uses 1, 4-diamino-anthraquinone leuco as a main raw material and sequentially carries out chlorination reaction, esterification reaction, sulfonation reaction and cyanidation reaction to obtain a finished product, and is characterized in that hydrogen chloride gas and sulfur dioxide gas generated by the chlorination reaction are removed by a blast air or reduced pressure method after the chlorination reaction, then the esterification reaction is directly carried out, the used solvent is a chlorobenzene organic solvent used for the chlorination reaction, and the weight ratio of concentrated sulfuric acid to 1, 4-diamino-2, 3-dichloroanthraquinone is 0.1: 1-1.5: 1.
2. The process for producing 1, 4-diamino-2, 3-dicyanoanthraquinone according to claim 1, wherein the water produced in the reaction is distilled off in the esterification reaction, and the portion of the organic solvent lost with the evaporation is added to the system.
3. The process for producing 1, 4-diamino-2, 3-dicyanoanthraquinone according to claim 1, wherein a quaternary ammonium salt as a catalyst is further added at the time of esterification.
4. The process for the preparation of 1, 4-diamino-2, 3-dicyanoanthraquinone according to claim 1, wherein after the sulfonation reaction, the organic solvent is recovered by a blowing-steaming method.
5. The process for producing 1, 4-diamino-2, 3-dicyanoanthraquinone according to claim 1, wherein the organic solvent is recovered by blowing and steaming at the same time of sulfonation.
6. The process according to any one of claims 1 to 5, wherein the weight ratio of concentrated sulfuric acid to 1, 4-diamino-2, 3-dichloroanthraquinone is 0.6: 1 to 0.8: 1.
7. The process according to claim 3, wherein the quaternary ammonium salt is benzyltriethylammonium chloride, dodecyltrimethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide or triphenylmethylammonium chloride, and the weight of the quaternary ammonium salt is 0.01: 1-0.05: 1 compared with 1, 4-diamino-2, 3-dichloroanthraquinone.
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| CN97106842A CN1069896C (en) | 1997-01-28 | 1997-01-28 | Process for preparing 1,4-diamino-2,3-dicyan anthraquinone |
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| CN1069896C true CN1069896C (en) | 2001-08-22 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US479521A (en) * | 1892-07-26 | Spirit-level for measuring-tapes | ||
| US4279825A (en) * | 1978-10-26 | 1981-07-21 | Bayer Aktiengesellschaft | Process for the preparation of 1,4-diaminoanthraquinone-2,3-disulphonic acid |
| CN1085210A (en) * | 1992-07-08 | 1994-04-13 | Basf公司 | Preparation of 1,4-diaminoanthraquinone-2,3-disulfonic acid and 1,4-diaminoanthraquinone-2,3-dinitrile |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US479521A (en) * | 1892-07-26 | Spirit-level for measuring-tapes | ||
| US4279825A (en) * | 1978-10-26 | 1981-07-21 | Bayer Aktiengesellschaft | Process for the preparation of 1,4-diaminoanthraquinone-2,3-disulphonic acid |
| CN1085210A (en) * | 1992-07-08 | 1994-04-13 | Basf公司 | Preparation of 1,4-diaminoanthraquinone-2,3-disulfonic acid and 1,4-diaminoanthraquinone-2,3-dinitrile |
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| Publication number | Publication date |
|---|---|
| CN1163262A (en) | 1997-10-29 |
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