CN109776339A - A kind of green synthesis method of 1,4-diaminoanthraquinone - Google Patents
A kind of green synthesis method of 1,4-diaminoanthraquinone Download PDFInfo
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- CN109776339A CN109776339A CN201910154300.8A CN201910154300A CN109776339A CN 109776339 A CN109776339 A CN 109776339A CN 201910154300 A CN201910154300 A CN 201910154300A CN 109776339 A CN109776339 A CN 109776339A
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Abstract
一种1,4‑二氨基蒽醌的绿色合成方法，涉及化学合成。氢化：以1,4‑二羟基蒽醌为原料，活性炭负载的PdRu双金属催化剂为加氢催化剂，在有机溶剂存在的条件下进行催化加氢反应，得加氢液；氨化：将得到的加氢液与氨气反应，反应结束后排出氨气，蒸发溶剂后得1,4‑二氨基蒽醌隐色体；氧化：在空气中将得到的1，4‑二氨基蒽醌隐色体加热反应后得到1,4‑二氨基蒽醌。采用纳米加氢还原工艺，合成工艺过程具有不产生高COD、高盐废水，不产生废酸，绿色环保。加氢催化剂可多次套用，反应溶剂可回收，生产成本低。产品纯度≥97％、收率≥95％，经济价值高。A green synthesis method of 1,4-diaminoanthraquinone relates to chemical synthesis. Hydrogenation: using 1,4-dihydroxyanthraquinone as a raw material, a PdRu bimetallic catalyst supported by activated carbon as a hydrogenation catalyst, and carrying out a catalytic hydrogenation reaction in the presence of an organic solvent to obtain a hydrogenation liquid; Amination: the obtained The hydrogenation liquid is reacted with ammonia gas, the ammonia gas is discharged after the reaction is finished, and the leuco 1,4-diaminoanthraquinone is obtained after evaporating the solvent; After the heating reaction, 1,4-diaminoanthraquinone is obtained. The nano-hydrogenation reduction process is adopted, and the synthesis process has the advantages of not producing high COD, high-salt wastewater, and no waste acid, which is green and environmentally friendly. The hydrogenation catalyst can be applied repeatedly, the reaction solvent can be recovered, and the production cost is low. The product purity is ≥97%, the yield is ≥95%, and the economic value is high.
Description
Technical field
The present invention relates to chemical syntheses, more particularly, to a kind of green synthesis method of Isosorbide-5-Nitrae-diamino-anthraquinone.
Background technique
Isosorbide-5-Nitrae-diamino-anthraquinone is the important intermediate of Dyestuff synthesis, be widely used in disperse dyes, reducing dye and
The production of acid dyes.Its committed step is the synthesis of 1,4- diamino-anthraquinone leuco compound.It industrially synthesizes extensively at present
Method under the conditions of existing for the sodium hydrosulfite or hydrazine hydrate, is generated with ammonium hydroxide single step reaction using Isosorbide-5-Nitrae-dihydroxy anthraquinone as raw material
Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound aoxidizes using oleum and generates Isosorbide-5-Nitrae-diamino-anthraquinone.But the disadvantages of the method are as follows
The spent acid of a large amount of high COD, high-salt wastewater and high COD is generated, spent acid and high-salt wastewater processing are difficult.
Chinese patent CN108395381A discloses a kind of preparation method of Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound, this method with 1,
4- dihydroxy anthraquinone is raw material, is mixed with hydrazine hydrate and organic solvent, in 0.2~0.5MPa of reaction pressure, reaction temperature 50~
Under the conditions of 100 DEG C, reacted with ammonia to prepare Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound, the disadvantages of the method are as follows the toxicity of hydrazine hydrate compared with
It is big and expensive.
Therefore, there is an urgent need in the art to a kind of new environmentally protective, inexpensive Isosorbide-5-Nitrae-diamino-anthraquinone procrypsis synthesis
Method.
Summary of the invention
In view of the above shortcomings of the prior art, the purpose of the present invention is to provide one kind that no waste water, spent acid generate
The green synthesis method of 1,4- diamino-anthraquinone.
The present invention the following steps are included:
1) hydrogenate: using Isosorbide-5-Nitrae-dihydroxy anthraquinone as raw material, activated carbon supported PdRu bimetallic catalyst is hydrogenation catalyst
Agent carries out catalytic hydrogenation reaction under the conditions of existing for the organic solvent, obtains hydrogenation liquid；
In step 1), the activated carbon supported PdRu bimetallic catalyst size can be 2~5nm, Pd/Ru atomicity
Ratio can be 1 ︰ (1~0.1)；The mass ratio of the hydrogenation catalyst and 1,4- dihydroxy anthraquinone can be (0.01~0.1) ︰ 1；Institute
The mass percentage concentration for stating 1,4- dihydroxy anthraquinone can be 10%~30%；The temperature of the catalytic hydrogenation reaction can be 40~90
DEG C, the pressure of reaction can be 0.2~1.0MPa；Solvent selected by the catalytic hydrogenation reaction can be selected from toluene, methanol, second
At least one of alcohol, DMSO, DMF etc..
2) ammonification: the hydrogenation liquid that step 1) is obtained is reacted with ammonia, and ammonia is discharged after reaction, is obtained after evaporating solvent
1,4- diamino-anthraquinone leuco compound；
In step 2), the ammonia and Isosorbide-5-Nitrae-dihydroxy anthraquinone mass ratio can be (0.1~0.5) ︰ 1；Described plus hydrogen
The temperature that liquid is reacted with ammonia can be 40~100 DEG C, preferably 60~80 DEG C, the pressure of reaction can 0.3~0.8MPa, reaction when
Between can be 1~4h.
3) it aoxidizes: obtaining Isosorbide-5-Nitrae-two after in air reacting Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound heating that step 2) obtains
Amino anthraquinones.
In step 3), the time of the heating reaction can be 1h.
Protrusion technical effect of the invention is given below:
Big for Isosorbide-5-Nitrae-diamino-anthraquinone synthesis technology wastewater flow rate, the problems such as low yield, one aspect of the present invention is to create
Activated carbon supported PdRu duplex metal nano granule replaces traditional one step ammonification technique of sodium hydrosulfite/hydrazine hydrate as catalyst
It is changed to and hydrogen and ammonification two is added to walk greatly, due to the unique effect of catalyst, and the path entirely reacted and intermediate product change；
On the other hand, the present invention substitutes traditional oleum oxidation technology with air oxidation.Specifically, it has the advantage that
1) nano hydrogenation reducing process is used, synthesis process, which has, does not generate high COD, high-salt wastewater, does not generate useless
Acid, it is environmentally protective.
2) hydrogenation catalyst can be applied repeatedly, and reaction dissolvent is recyclable, and production cost is low.
3) product purity >=97%, yield >=95%, economic value are high.
Detailed description of the invention
Fig. 1 is that HPLC analyzes 1,4- diamino-anthraquinone product purity 98.3%.
Specific embodiment
Following embodiment will the present invention is further illustrated in conjunction with attached drawing.
Embodiment 1:
It is 1% that 8g1,4- dihydroxy anthraquinone, 100mL toluene and 0.6g palladium content are put into 500mL autoclave
Pd10Ru1/ C catalyst is 40 DEG C in reaction temperature, and reaction pressure carries out catalytic hydrogenation reaction under conditions of being 1.0MPa, reacts
After filter out catalyst and obtain hydrogenation liquid, under conditions of 40 DEG C of reaction temperature, reaction pressure 0.8MPa, hydrogenation liquid and ammonia
Excessive ammonia is discharged in solid/liquid/gas reactions 2h after reaction, and heating evaporation obtains Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound after falling toluene, so
Afterwards Isosorbide-5-Nitrae-diamino-anthraquinone will be obtained after Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound heating reaction 1h in air.It is pure that HPLC analyzes product
Degree 98.3%, calculated yield 95%, as shown in Figure 1.
Embodiment 2:
It is 1% that 10g 1,4- dihydroxy anthraquinone, 200mL ethyl alcohol and 1.0g palladium content are put into 500mL autoclave
Pd1Ru1/ C catalyst is 90 DEG C in reaction temperature, and reaction pressure carries out catalytic hydrogenation reaction under conditions of being 0.4MPa, instead
Catalyst is filtered out after answering obtains hydrogenation liquid, under conditions of 100 DEG C of reaction temperature, reaction pressure 0.3MPa, hydrogenation liquid
4h is reacted with ammonia, excessive ammonia is discharged after reaction, and heating evaporation obtains Isosorbide-5-Nitrae-diamino-anthraquinone procrypsis after falling ethyl alcohol
Then body will obtain Isosorbide-5-Nitrae-diamino-anthraquinone after Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound heating reaction 1h in air.With HPLC points
Analyse product purity 96.7%, calculated yield 96%.
Embodiment 3:
It is 1% that 40g 1,4- dihydroxy anthraquinone, 300mL toluene and 2g palladium content are put into 1000mL autoclave
PdRu2/ C catalyst is 60 DEG C in reaction temperature, and reaction pressure carries out catalytic hydrogenation reaction under conditions of being 0.6MPa, reacts
After filter out catalyst and obtain hydrogenation liquid, under conditions of 60 DEG C of reaction temperature, reaction pressure 0.6MPa, hydrogenation liquid and ammonia
Ammonia is discharged in solid/liquid/gas reactions 1h after reaction, and heating evaporation obtains Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound after falling toluene, then in sky
In gas Isosorbide-5-Nitrae-diamino-anthraquinone will be obtained after Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound heating reaction 3h.Product purity is analyzed with HPLC
97.2%, calculated yield 96%.
Embodiment 4:
Catalyst in embodiment 2 is applied, 40g Isosorbide-5-Nitrae-dihydroxy-anthracene is put into 1000mL autoclave
The PdRu that used palladium content is 1% in quinone, 300mL toluene and 2g embodiment 22/ C catalyst is 500 DEG C in reaction temperature,
Reaction pressure carries out catalytic hydrogenation reaction under conditions of being 0.8MPa, filters out catalyst after reaction and obtains hydrogenation liquid,
70 DEG C of reaction temperature, under conditions of reaction pressure 0.5MPa, hydrogenation liquid reacts 3h with ammonia, and ammonia is discharged after reaction, adds
Thermal evaporation obtains Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound after falling toluene, then in air heats Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound
1,4- diamino-anthraquinone is obtained after reaction 0.5h.Product purity 97.5%, calculated yield 97% are analyzed with HPLC.
The present invention using Isosorbide-5-Nitrae-dihydroxy anthraquinone as raw material, successively by palladium base nanocatalyst hydrogenating reduction, aminating reaction,
Oxidation reaction obtains Isosorbide-5-Nitrae-diamino-anthraquinone.The present invention, which has, not to be generated high COD, high-salt wastewater, not to generate spent acid and green ring
The advantages that guarantor.In addition to this, reaction dissolvent is recyclable recycles, and high product purity, high income are suitble to industrial production.
Claims (10)
1. a kind of green synthesis method of Isosorbide-5-Nitrae-diamino-anthraquinone, it is characterised in that the following steps are included:
1) hydrogenate: using Isosorbide-5-Nitrae-dihydroxy anthraquinone as raw material, activated carbon supported PdRu bimetallic catalyst is hydrogenation catalyst,
Catalytic hydrogenation reaction is carried out under the conditions of organic solvent is existing, obtains hydrogenation liquid；
2) ammonification: the hydrogenation liquid that step 1) is obtained is reacted with ammonia, and ammonia is discharged after reaction, obtains Isosorbide-5-Nitrae-after evaporating solvent
Diamino-anthraquinone leuco compound；
3) it aoxidizes: obtaining Isosorbide-5-Nitrae-diamino after in air reacting Isosorbide-5-Nitrae-diamino-anthraquinone leuco compound heating that step 2) obtains
Anthraquinone.
2. a kind of green synthesis method of Isosorbide-5-Nitrae-diamino-anthraquinone as described in claim 1, it is characterised in that in step 1), institute
Activated carbon supported PdRu bimetallic catalyst is stated having a size of 2~5nm, Pd/Ru atomicity ratio is 1 ︰ (1~0.1).
3. a kind of green synthesis method of Isosorbide-5-Nitrae-diamino-anthraquinone as described in claim 1, it is characterised in that in step 1), institute
The mass ratio for stating hydrogenation catalyst and 1,4- dihydroxy anthraquinone is (0.01~0.1) ︰ 1.
4. a kind of green synthesis method of Isosorbide-5-Nitrae-diamino-anthraquinone as described in claim 1, it is characterised in that in step 1), institute
The mass percentage concentration for stating 1,4- dihydroxy anthraquinone is 10%~30%.
5. a kind of green synthesis method of Isosorbide-5-Nitrae-diamino-anthraquinone as described in claim 1, it is characterised in that in step 1), institute
The temperature for stating catalytic hydrogenation reaction is 40~90 DEG C, and the pressure of reaction is 0.2~1.0MPa.
6. a kind of green synthesis method of Isosorbide-5-Nitrae-diamino-anthraquinone as described in claim 1, it is characterised in that in step 1), institute
It states solvent selected by catalytic hydrogenation reaction and is selected from least one of toluene, methanol, ethyl alcohol, DMSO, DMF.
7. a kind of green synthesis method of Isosorbide-5-Nitrae-diamino-anthraquinone as described in claim 1, it is characterised in that in step 2), institute
The mass ratio for stating ammonia and 1,4- dihydroxy anthraquinone is (0.1~0.5) ︰ 1.
8. a kind of green synthesis method of Isosorbide-5-Nitrae-diamino-anthraquinone as described in claim 1, it is characterised in that in step 2), institute
Stating the temperature that hydrogenation liquid is reacted with ammonia is 40~100 DEG C, 0.3~0.8MPa of pressure of reaction, and the time of reaction is 1~4h.
9. a kind of green synthesis method of Isosorbide-5-Nitrae-diamino-anthraquinone as claimed in claim 8, it is characterised in that the hydrogenation liquid with
The temperature of ammonia reaction is 60~80 DEG C.
10. a kind of green synthesis method of Isosorbide-5-Nitrae-diamino-anthraquinone as described in claim 1, it is characterised in that in step 3),
The time of the heating reaction is 1h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082176A (en) * | 2022-12-28 | 2023-05-09 | 宁夏建鹏新材料科技有限公司 | A new method for the synthesis of 1,4-diaminoanthraquinone |
| CN116082219A (en) * | 2022-08-11 | 2023-05-09 | 山东大学 | A kind of preparation method based on disperse blue 60 disperse dye |
| CN119019273A (en) * | 2024-08-15 | 2024-11-26 | 湖南人文科技学院 | A method for synthesizing 1,4-diaminoanthraquinone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017039A (en) * | 2015-07-15 | 2015-11-04 | 扬州日兴生物科技股份有限公司 | Continuous preparation method of 1-aminoanthraquinone |
| CN106748902A (en) * | 2016-12-30 | 2017-05-31 | 江苏道博化工有限公司 | One kind 1 amino 4 of synthesis（Ethylamino）The method of the sulfonic acid of 9,10 anthraquinone 2 |
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2019
- 2019-03-01 CN CN201910154300.8A patent/CN109776339B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017039A (en) * | 2015-07-15 | 2015-11-04 | 扬州日兴生物科技股份有限公司 | Continuous preparation method of 1-aminoanthraquinone |
| CN106748902A (en) * | 2016-12-30 | 2017-05-31 | 江苏道博化工有限公司 | One kind 1 amino 4 of synthesis（Ethylamino）The method of the sulfonic acid of 9,10 anthraquinone 2 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082219A (en) * | 2022-08-11 | 2023-05-09 | 山东大学 | A kind of preparation method based on disperse blue 60 disperse dye |
| CN116082219B (en) * | 2022-08-11 | 2024-04-26 | 山东大学 | A preparation method based on disperse blue 60 disperse dye |
| CN116082176A (en) * | 2022-12-28 | 2023-05-09 | 宁夏建鹏新材料科技有限公司 | A new method for the synthesis of 1,4-diaminoanthraquinone |
| CN116082176B (en) * | 2022-12-28 | 2024-11-08 | 宁夏建鹏新材料科技有限公司 | A new method for synthesizing 1,4-diaminoanthraquinone |
| CN119019273A (en) * | 2024-08-15 | 2024-11-26 | 湖南人文科技学院 | A method for synthesizing 1,4-diaminoanthraquinone |
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