CN104892426A - Method for preparing 1-nitroanthraquinone by using pyrrolidinone ionic liquid as catalyst - Google Patents
Method for preparing 1-nitroanthraquinone by using pyrrolidinone ionic liquid as catalyst Download PDFInfo
- Publication number
- CN104892426A CN104892426A CN201510290185.9A CN201510290185A CN104892426A CN 104892426 A CN104892426 A CN 104892426A CN 201510290185 A CN201510290185 A CN 201510290185A CN 104892426 A CN104892426 A CN 104892426A
- Authority
- CN
- China
- Prior art keywords
- nitroanthraquinone
- anthraquinone
- reaction
- ionic liquid
- catalyst
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of anthraquinone dye intermediate synthesis, and particularly relates to a method for preparing 1-nitroanthraquinone through location nitration by using pyrrolidinone ionic liquid as a catalyst. The method comprises the step of preparing the 1-nitroanthraquinone by using anthraquinone and a nitration agent as raw materials and using the pyrrolidinone ionic liquid as the catalyst. The method has the advantages that the purity of the crude 1-nitroanthraquinone product obtained in a catalytic nitration process is increased to 90% or more, the catalyst preparation is simple, the cost is reduced, and the quantity of solid waste residues generated in a refinement process is reduced.
Description
Technical field
The present invention relates to a kind of with pyrrolidinone compounds ionic liquid for catalyzer location nitration prepares the method for 1-nitroanthraquinone, belong to anthraquinone dye intermediate synthesis technical field.
Background technology
1-nitroanthraquinone is important dyestuff intermediate, is also the important source material of synthesis 1-aminoanthraquinone simultaneously.The method of initial production 1-nitroanthraquinone is mercury localization method, but brings serious environmental pollution in process of production due to this method, is eliminated.The method of the current 1-of preparation nitroanthraquinone mainly contains the direct nitrofication process of anthraquinone, naphthoquinones method, the direct nitrofication process of phthalic anhydride, anthrone method etc.; Wherein the direct nitrofication process of anthraquinone is the most conventional, but when the subject matter existed is mixed acid nitrification technology side reaction many and crude product refining, yield is low.
The method of a kind of nitrogen pentoxide nitrated synthesis 1-nitroanthraquinone is disclosed in patent CN103435492A, the method is carry out in the nitrated system of the organic solvent of catalyzer at nitrogen pentoxide, the content preparing the 1-nitroanthraquinone in the itrated compound of gained reaches more than 85%, there is the features such as reaction conditions gentleness, selectivity be better, but its reaction conversion ratio is very low, catalyzer reusability is poor, is not suitable for industrialization promotion.
A kind of production technique of high-purity 1-nitroanthraquinone is disclosed in patent CN102557956A, taking solid acid as catalyzer, 1,2-ethylene dichloride is solvent, and nitrosonitric acid is nitrating agent, and reaction has good selectivity, the mass percentage of 1-nitroanthraquinone reaches 86.5%, but catalyst preparing is complicated, and cost is higher, and do not report that situation reused by catalyzer.
Disclosing a kind of in patent CN104030927A take metal modified molecular screen as the method for catalyst preparing 1-nitroanthraquinone, the method specifically comprises: (1) to be mixed with anthraquinone, metal modified molecular screen catalyzer, acid promotor and solvent reaction substrate in heating condition under continous way add nitrating agent, treat nitrating agent add after the isothermal reaction some time; (2) reaction product is carried out purification process.Adopt metal-modified molecular sieve, very big raising nitro is in the replacement of the orienting station of the contiguous Sauerstoffatom of anthracene nucleus, reduce nitro in the replacement probability of other position of anthracene nucleus, reduce byproduct thus, the purity of 1-nitroanthraquinone product can be made to improve and reach about 93%; Add the promotor of acid, the transformation efficiency of nitration reaction is improved.But the directional catalyst molecular sieve used needs high-temperature activation, need to carry out modification by the halogenide of metallic tin, palladium, gold etc. or other salt simultaneously, and add mineral acid or organic acid as promotor, technics comparing is complicated, and catalyzer cost is high.
Summary of the invention
The object of the invention is to overcome that the catalyst preparation process existed in prior art is complicated, cost is high, need to add mineral acid or organic acid as shortcomings such as promotors, and provide a kind of employing with low cost, the method preparing 1-nitroanthraquinone of the catalyzer that can reuse.
A kind of with the method for pyrrolidinone compounds ionic liquid for catalyst preparing 1-nitroanthraquinone, it is characterized in that carrying out according to following step: in reaction vessel, add anthraquinone, catalysts and solvents, warming-in-water is to material 20 ~ 45 DEG C, start to add nitrating agent, controlling temperature of reaction in adition process is 20 ~ 60 DEG C; Finish, at 20 ~ 60 DEG C, insulation reaction is less than 2% for reaction end to sampling detection anthraquinone content; Arrive after reaction end, reaction solution through washing, neutralization, air distillation recycling design, filter, drain and obtain after drying 1-nitroanthraquinone crude product;
Wherein said catalyzer is pyrrolidinone compounds ionic liquid, and chemical structure of general formula is as follows:
Wherein m represents the integer of 0 to 8, and R is H or C
1 ~ 12alkyl, C
2 ~ 6hydroxyalkyl or C
2 ~ 6thiazolinyl, preferred m=0,3 or 4; Wherein said catalyst levels is the 0.01wt% ~ 10wt% of anthraquinone quality.
X
-for the one in bisulfate ion, dihydrogen phosphate, p-methyl benzenesulfonic acid root, trifluoromethayl sulfonic acid root, methylsulphonic acid root, formate or acetate.
Preferably, add in the process of nitrating agent, controlling temperature of reaction is 39 ~ 44 DEG C.
Preferably, the time adding nitrating agent is 1 ~ 6h.
Preferably, the insulation reaction time is 1 ~ 10 hour.
Preferably, the method that described sampling detects anthraquinone content is high performance liquid chromatography.
Preferably, described solvent is one or more in the halogenated alkanes such as 1,2-ethylene dichloride, methylene dichloride, tetracol phenixin or chloroform.
Preferably, described nitrating agent is nitric acid, nitryl chloride, nitryl bromine, nitrogen peroxide or nitrogen pentoxide.
Preferably, described add anthraquinone, catalyzer, solvent, nitrating agent mass ratio be 1:0.01 ~ 0.1:1.0 ~ 1.5:0.3 ~ 0.5.
Another object of the present invention is to the purposes providing described pyrrolidinone compounds ionic liquid, its location nitration for catalysis anthraquinone reacts.
Preferably, the chemical structure of general formula of described pyrrolidinone compounds ionic liquid is as follows:
Wherein m represents the integer of 0 to 8, and R is H or C
1 ~ 12alkyl, C
2 ~ 6hydroxyalkyl or C
2 ~ 6thiazolinyl;
X
-for the one in bisulfate ion, dihydrogen phosphate, p-methyl benzenesulfonic acid root, trifluoromethayl sulfonic acid root, methylsulphonic acid root, formate or acetate.
Preferably, in the location nitration reaction of described catalysis anthraquinone, wherein said pyrrolidinone compounds ionic liquid consumption is the 0.01wt% ~ 10wt% of anthraquinone quality.
Advantage of the present invention is: adopt the purity of the nitrated thick 1-nitroanthraquinone product obtained of pyrrolidinone compounds ionic liquid directional catalyzing to bring up to more than 90%, do not use mineral acid, organic acid as promotor, thus significantly reduce cost, decrease the generation of solid slag in treating process.
Embodiment
Several pyrrolidinone compounds ionic liquid can be used as catalyzer below, and location nitration prepares 1-nitroanthraquinone, and described pyrrolidinone compounds ionic liquid has following chemical structural formula, is expressed as follows formula:
Embodiment 1:
In a kettle., anthraquinone 100g, catalyst I 5g, 1,2-ethylene dichloride 120g (anthraquinone: catalyst I: ethylene dichloride=100:5:100) is added; Warming-in-water, to material 40 DEG C, starts to drip 98% concentrated nitric acid 40g, accurately controls temperature of reaction and maintains 40 ~ 42 DEG C, within 4 hours, add nitric acid.Finish, in 40 DEG C of insulation reaction 4 hours, sampling high performance liquid chromatography detected anthraquinone content and is less than 2% for reaction end; After terminal arrives, the 300ml that adds water immediately dilutes, and after stirring, incline waste acid water, then adds isodose water washing material 2 times, and finally, add water 300ml, adjusts material pH=6.5 ~ 7.5 with 30% sodium hydroxide solution.Material web water is transferred in the glass reaction still of 500ml, open steam heating, open the valve towards condenser, Distillation recovery ethylene dichloride, cool to about 30 ~ 40 DEG C, obtain 1-nitroanthraquinone crude product after separating treatment, pass through efficient liquid phase chromatographic analysis, the content of 1-nitroanthraquinone reaches 95.13%, and transformation efficiency reaches 97.25%.
Embodiment 2:
In a kettle., anthraquinone 100g, catalyst I I3.5g, 1,2-ethylene dichloride 130g (anthraquinone: catalyst I I: ethylene dichloride=100:3.5:130) is added; Warming-in-water, to material 30 DEG C, starts to drip 98% concentrated nitric acid 36g, accurately controls temperature of reaction 40 ~ 42 DEG C, within 4 hours, adds nitric acid.Finish, in 40 DEG C of insulation reaction 4 hours, sampling high performance liquid chromatography detects anthraquinone content and is less than 2%, and after terminal arrives, the 300ml that adds water immediately dilutes, after stirring, incline waste acid water, then add isodose water washing material 2 times, finally, add water 300ml, adjusts material pH=6.5 ~ 7.5 with 30% sodium hydroxide solution.Material web water is transferred in the glass reaction still of 500ml, open steam heating, open the valve towards condenser, Distillation recovery ethylene dichloride, cool to about 30 ~ 40 DEG C, obtain 1-nitroanthraquinone crude product after separating treatment, pass through efficient liquid phase chromatographic analysis, the content of 1-nitroanthraquinone reaches 93.27%, and transformation efficiency reaches 96.25%.
Embodiment 3:
In a kettle., anthraquinone 100g, catalyst I II4.5g, 1,2-ethylene dichloride 120g (anthraquinone: catalyst I II: ethylene dichloride=100:4.5:120) is added.Warming-in-water, to material 40 DEG C, accurately controls temperature of reaction 40 ~ 42 DEG C, within 4 hours, passes into nitryl chloride 46g.Finish, in 40 DEG C of insulation reaction 4 hours, sampling high performance liquid chromatography detects anthraquinone content and is less than 2%, and after terminal arrives, the 300ml that adds water immediately dilutes, after stirring, incline waste acid water, then add isodose water washing material 2 times, finally, add water 300ml, adjusts material pH=6.5 ~ 7.5 with 30% sodium hydroxide solution.Material web water is transferred in the glass reaction still of 500ml, open steam heating, open the valve towards condenser, Distillation recovery ethylene dichloride, cool to about 30 ~ 40 DEG C, obtain 1-nitroanthraquinone crude product after separating treatment, pass through efficient liquid phase chromatographic analysis, the content of 1-nitroanthraquinone reaches 93.21%, and transformation efficiency reaches 94.58%.
Embodiment 4:
In a kettle., anthraquinone 100g, catalyst I V1.5g, 1,2-ethylene dichloride 120g (anthraquinone: catalyst I V: ethylene dichloride=100:1.5:150) is added.Warming-in-water, to material 20 DEG C, accurately controls temperature of reaction 20 ~ 22 DEG C, passes into dry O in 6 hours
3/ NO
2mixed gas to reaction solution sampling high performance liquid chromatography detects anthraquinone content and is less than 2%, and wherein in mixed gas, the mol ratio of ozone and nitrogen peroxide is 2:1.After terminal arrives, the 300ml that adds water immediately dilutes, and after stirring, incline waste acid water, then adds isodose water washing material 2 times, and finally, add water 300ml, adjusts material pH=6.5 ~ 7.5 with 30% sodium hydroxide solution.Material web water is transferred in the glass reaction still of 500ml, open steam heating, open the valve towards condenser, Distillation recovery ethylene dichloride, cool to about 30 ~ 40 DEG C, obtain 1-nitroanthraquinone crude product after separating treatment, pass through efficient liquid phase chromatographic analysis, the content of 1-nitroanthraquinone reaches 90.32%, and transformation efficiency reaches 93.24%.
Embodiment 5:
In a kettle., anthraquinone 100g, catalyst V 7g, tetracol phenixin 120g (anthraquinone: catalyst V: tetracol phenixin=100:7:120) is added.Warming-in-water, to material 40 DEG C, starts to drip 98% concentrated nitric acid 36g, accurately controls temperature of reaction 40 ~ 42 DEG C, within 4 hours, adds nitric acid.Finish, in 40 DEG C of insulation reaction 4 hours, sampling high performance liquid chromatography detects anthraquinone content and is less than 2%, and after terminal arrives, the 300ml that adds water immediately dilutes, after stirring, incline waste acid water, then add isodose water washing material 2 times, finally, add water 300ml, adjusts material pH=6.5 ~ 7.5 with 30% sodium hydroxide solution.Material web water is transferred in the glass reaction still of 500ml, open steam heating, open the valve towards condenser, Distillation recovery tetracol phenixin, cool to about 30 ~ 40 DEG C, obtain 1-nitroanthraquinone crude product after separating treatment, pass through efficient liquid phase chromatographic analysis, the content of 1-nitroanthraquinone reaches 94.27%, and transformation efficiency reaches 96.23%.
Embodiment 6:
In a kettle., add anthraquinone 100g, catalyst V I 3g, solvent 120g, solvent is the mixed solvent (anthraquinone: catalyst V I: solvent=100:3:120) of ethylene dichloride 80g and methylene dichloride 40g.Warming-in-water, to material 45 DEG C, starts to drip 98% concentrated nitric acid 36g, accurately controls temperature of reaction 60 ~ 62 DEG C, within 4 hours, adds nitric acid.Finish, in 60 DEG C of insulation reaction 1 hour, sampling high performance liquid chromatography detects anthraquinone content and is less than 2%, and after terminal arrives, the 300ml that adds water immediately dilutes, after stirring, incline waste acid water, then add isodose water washing material 2 times, finally, add water 300ml, adjusts material pH=6.5 ~ 7.5 with 30% sodium hydroxide solution.Material web water is transferred in the glass reaction still of 500ml, open steam heating, open the valve towards condenser, Distillation recovery tetracol phenixin, cool to about 30 ~ 40 DEG C, obtain 1-nitroanthraquinone crude product after separating treatment, pass through efficient liquid phase chromatographic analysis, the content of 1-nitroanthraquinone reaches 92.32%, and transformation efficiency reaches 94.41%.
Embodiment 7:
In a kettle., anthraquinone 100g, catalyst V II1g, 1,2-ethylene dichloride 120g (anthraquinone: catalyst V II: ethylene dichloride=100:1:100) is added; Warming-in-water, to material 40 DEG C, starts to drip 98% concentrated nitric acid 40g, accurately controls temperature of reaction and maintains 40 ~ 42 DEG C, within 4 hours, add nitric acid.Finish, in 40 DEG C of insulation reaction 4 hours, sampling high performance liquid chromatography detected anthraquinone content and is less than 2% for reaction end; After terminal arrives, the 300ml that adds water immediately dilutes, and after stirring, incline waste acid water, then adds isodose water washing material 2 times, and finally, add water 300ml, adjusts material pH=6.5 ~ 7.5 with 30% sodium hydroxide solution.Material web water is transferred in the glass reaction still of 500ml, open steam heating, open the valve towards condenser, Distillation recovery ethylene dichloride, cool to about 30 ~ 40 DEG C, obtain 1-nitroanthraquinone crude product after separating treatment, pass through efficient liquid phase chromatographic analysis, the content of 1-nitroanthraquinone reaches 94.23%, and transformation efficiency reaches 96.89%.
Claims (10)
1. one kind with the method for pyrrolidinone compounds ionic liquid for catalyst preparing 1-nitroanthraquinone, it is characterized in that carrying out according to following step: in reaction vessel, add anthraquinone, catalysts and solvents, warming-in-water is to material 20 ~ 45 DEG C, start to add nitrating agent, controlling temperature of reaction in adition process is 20 ~ 60 DEG C; Finish, at 20 ~ 60 DEG C, insulation reaction is less than 2% for reaction end to sampling detection anthraquinone content; Arrive after reaction end, reaction solution through washing, neutralization, air distillation recycling design, filter, drain and obtain after drying 1-nitroanthraquinone crude product;
Wherein said catalyzer is pyrrolidinone compounds ionic liquid, and chemical structure of general formula is as follows:
Wherein m represents the integer of 0 to 8, and R is H or C
1 ~ 12alkyl, C
2 ~ 6hydroxyalkyl or C
2 ~ 6thiazolinyl; Wherein said catalyst levels is the 0.01wt% ~ 10wt% of anthraquinone quality;
X
-for the one in bisulfate ion, dihydrogen phosphate, p-methyl benzenesulfonic acid root, trifluoromethayl sulfonic acid root, methylsulphonic acid root, formate or acetate.
2. the method preparing 1-nitroanthraquinone according to claim 1, is characterized in that described m=0,3 or 4.
3. the method preparing 1-nitroanthraquinone according to claim 1, adds described in it is characterized in that in the process of nitrating agent, and controlling temperature of reaction is 39 ~ 44 DEG C.
4. the method preparing 1-nitroanthraquinone according to any one of claim 1-3, is characterized in that described solvent is one or more in 1,2-ethylene dichloride, methylene dichloride, tetracol phenixin or chloroform.
5. the method preparing 1-nitroanthraquinone according to any one of claim 1-3, is characterized in that described nitrating agent is nitric acid, nitryl chloride, nitryl bromine, nitrogen peroxide or nitrogen pentoxide.
6. the method preparing 1-nitroanthraquinone according to any one of claim 1-3, it is characterized in that described add anthraquinone, catalyzer, solvent, nitrating agent mass ratio be 1:0.01 ~ 0.1:1.0 ~ 1.5:0.3 ~ 0.5.
7. the method preparing 1-nitroanthraquinone according to any one of claim 1-3, is characterized in that the described insulation reaction time is 1 ~ 10 hour.
8. the purposes of pyrrolidinone compounds ionic liquid, is characterized in that its location nitration for catalysis anthraquinone reacts.
9. the purposes of pyrrolidinone compounds ionic liquid according to claim 8, is characterized in that the chemical structure of general formula of pyrrolidinone compounds ionic liquid is as follows:
Wherein m represents the integer of 0 to 8, and R is H or C
1 ~ 12alkyl, C
2 ~ 6hydroxyalkyl or C
2 ~ 6thiazolinyl;
X
-for the one in bisulfate ion, dihydrogen phosphate, p-methyl benzenesulfonic acid root, trifluoromethayl sulfonic acid root, methylsulphonic acid root, formate or acetate.
10. the purposes of pyrrolidinone compounds ionic liquid according to claim 7, is characterized in that wherein said pyrrolidinone compounds ionic liquid consumption is the 0.01wt% ~ 10wt% of anthraquinone quality in the location nitration reaction of described catalysis anthraquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510290185.9A CN104892426B (en) | 2015-05-29 | 2015-05-29 | A kind of method using pyrrolidinone compounds ionic liquid as the nitroanthraquinone of catalyst preparation 1 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510290185.9A CN104892426B (en) | 2015-05-29 | 2015-05-29 | A kind of method using pyrrolidinone compounds ionic liquid as the nitroanthraquinone of catalyst preparation 1 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104892426A true CN104892426A (en) | 2015-09-09 |
| CN104892426B CN104892426B (en) | 2018-01-30 |
Family
ID=54025450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510290185.9A Active CN104892426B (en) | 2015-05-29 | 2015-05-29 | A kind of method using pyrrolidinone compounds ionic liquid as the nitroanthraquinone of catalyst preparation 1 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104892426B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108911999A (en) * | 2018-08-06 | 2018-11-30 | 朱晓萍 | A kind of synthetic method of 1- amino anthraquinones |
| CN112778789A (en) * | 2021-01-06 | 2021-05-11 | 贺潇寒 | Method for chlorinating blue anthrone, violanthrone or isoviolanthrone |
| CN113563196A (en) * | 2021-07-27 | 2021-10-29 | 安徽江泰新材料科技有限公司 | Preparation method of 2,4(2,6) -dimethyl nitrobenzene |
| CN115819289A (en) * | 2022-10-18 | 2023-03-21 | 浙江恒逸石化研究院有限公司 | Preparation method of anthraquinone-2-sulfonic acid compound |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030181780A1 (en) * | 2002-03-22 | 2003-09-25 | Konrad Herbst | Process for paraffin hydrocarbon isomerization and composite catalyst therefore |
| CN101024625A (en) * | 2007-03-23 | 2007-08-29 | 广东工业大学 | Ketopyrrolidine sulfurate in liquid and its prpearing method |
| EP1386907B1 (en) * | 2002-07-31 | 2011-10-05 | Council of Scientific and Industrial Research | Process for vapor phase nitration of benzene using nitric acid over molybdenum silica catalyst |
| CN102557956A (en) * | 2010-12-20 | 2012-07-11 | 江苏亚邦染料股份有限公司 | Production process of high-purity 1-nitroanthraquinone |
| CN104030927A (en) * | 2014-06-18 | 2014-09-10 | 江苏亚邦染料股份有限公司 | Method for preparing 1-nitroanthraquinone by using metal-modified molecular sieve as catalyst |
-
2015
- 2015-05-29 CN CN201510290185.9A patent/CN104892426B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030181780A1 (en) * | 2002-03-22 | 2003-09-25 | Konrad Herbst | Process for paraffin hydrocarbon isomerization and composite catalyst therefore |
| EP1386907B1 (en) * | 2002-07-31 | 2011-10-05 | Council of Scientific and Industrial Research | Process for vapor phase nitration of benzene using nitric acid over molybdenum silica catalyst |
| CN101024625A (en) * | 2007-03-23 | 2007-08-29 | 广东工业大学 | Ketopyrrolidine sulfurate in liquid and its prpearing method |
| CN102557956A (en) * | 2010-12-20 | 2012-07-11 | 江苏亚邦染料股份有限公司 | Production process of high-purity 1-nitroanthraquinone |
| CN104030927A (en) * | 2014-06-18 | 2014-09-10 | 江苏亚邦染料股份有限公司 | Method for preparing 1-nitroanthraquinone by using metal-modified molecular sieve as catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 陈海群 等: "《化工生产安全技术》", 31 January 2012 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108911999A (en) * | 2018-08-06 | 2018-11-30 | 朱晓萍 | A kind of synthetic method of 1- amino anthraquinones |
| CN108911999B (en) * | 2018-08-06 | 2021-05-04 | 朱晓萍 | Synthesis method of 1-aminoanthraquinone |
| CN112778789A (en) * | 2021-01-06 | 2021-05-11 | 贺潇寒 | Method for chlorinating blue anthrone, violanthrone or isoviolanthrone |
| CN112778789B (en) * | 2021-01-06 | 2021-11-12 | 贺潇寒 | Method for chlorinating blue anthrone, violanthrone or isoviolanthrone |
| WO2022147994A1 (en) * | 2021-01-06 | 2022-07-14 | 贺潇寒 | Method for chlorinating indanthrone blue, violanthrone or isoviolanthrone |
| US11939475B2 (en) | 2021-01-06 | 2024-03-26 | Xiaohan HE | Method for chlorinating blue anthrone, violanthrone or isoviolantrone |
| CN113563196A (en) * | 2021-07-27 | 2021-10-29 | 安徽江泰新材料科技有限公司 | Preparation method of 2,4(2,6) -dimethyl nitrobenzene |
| CN115819289A (en) * | 2022-10-18 | 2023-03-21 | 浙江恒逸石化研究院有限公司 | Preparation method of anthraquinone-2-sulfonic acid compound |
| CN115819289B (en) * | 2022-10-18 | 2024-04-05 | 浙江恒逸石化研究院有限公司 | Preparation method of anthraquinone-2-sulfonic acid compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104892426B (en) | 2018-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104892426A (en) | Method for preparing 1-nitroanthraquinone by using pyrrolidinone ionic liquid as catalyst | |
| CN101704824A (en) | Catalytic preparation method of dicyclopentadiene dioxide by quaternary ammonium heteropoly phosphato tungstate | |
| CN115368272A (en) | Preparation method of 4-cyano-2-methoxybenzaldehyde | |
| CN110668967B (en) | Photocatalytic preparation method of alpha-ketoamide compound | |
| CN109746042B (en) | Catalyst for synthesizing 3-methoxy methyl acrylate and solid-supported and using method | |
| CN104030927B (en) | A kind of method with metal modified molecular screen for catalyst preparing 1-nitroanthraquinone | |
| Wang et al. | Enhancing esterification of small molecular acids with alcohols by molten salt hydrates | |
| CN105017131B (en) | A kind of piperidine compounds and its preparation technology | |
| CN103804105A (en) | Synthesis method for biphenyl compounds | |
| CN104030925A (en) | Method for catalytically synthesizing mononitrochlorobenzene | |
| CN112707807B (en) | Preparation method of 4, 5-difluorophthalic acid | |
| CN105669413B (en) | A kind of method that microwave radiation prepares 2- methyl-1,4-naphthaquinone | |
| CN104059015A (en) | Method for synthesizing carbazole by fixed bed process | |
| CN107522606A (en) | Synthetic method of 2-methyl-4-carbonyl-2, 4-diphenylbutanal | |
| CN107573301B (en) | Preparation method of tricyclazole intermediate | |
| CN109575019B (en) | Preparation method of 5-bromo-7-azaindole | |
| CN112707860A (en) | Synthesis method of active intermediate 4-chloro-3-nitropyridine | |
| CN103408434B (en) | Method for synthesizing aniline by directly oxidizing and aminating benzene by one step | |
| CN106674162B (en) | Preparation method of 2, 5-furan diformaldehyde | |
| CN108752180B (en) | Method for preparing 1-chloroanthraquinone by direct chlorination of photocatalytic chlorine | |
| CN110668972A (en) | Preparation method of 3, 4-dimethoxy benzonitrile | |
| CN104059014A (en) | Method for preparing carbazole through catalysis of diphenylamine | |
| CN112457235B (en) | Preparation method of 7-methylindole | |
| CN107935876B (en) | Preparation method of 2- (3-amino-4-chlorobenzoyl) benzoic acid | |
| CN109369357B (en) | Method for preparing symmetrical diaryl ketone by catalytic oxidation carbonylation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201130 Address after: 223500 heggou town (Chemical Industrial Park), Ganyan County, Lianyungang, Jiangsu Patentee after: LIANYUNGANG BRANCH OF JIANGSU YABANG DYESTUFF Co.,Ltd. Address before: 213163, No. 105, Renmin West Road, Niu Tong Town, Wujin District, Jiangsu, Changzhou Patentee before: JIANGSU YABANG DYE Co.,Ltd. |