CN111116378A - Method for synthesizing 1, 8-diaminonaphthalene by selective reduction of 1, 8-dinitronaphthalene - Google Patents
Method for synthesizing 1, 8-diaminonaphthalene by selective reduction of 1, 8-dinitronaphthalene Download PDFInfo
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- CN111116378A CN111116378A CN201911327020.9A CN201911327020A CN111116378A CN 111116378 A CN111116378 A CN 111116378A CN 201911327020 A CN201911327020 A CN 201911327020A CN 111116378 A CN111116378 A CN 111116378A
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- dinitronaphthalene
- diaminonaphthalene
- selective reduction
- solvent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
Abstract
The invention discloses a method for preparing 1, 8-diaminonaphthalene by selectively reducing 1, 8-dinitronaphthalene, which is a method for only generating 1, 8-diaminonaphthalene by adding a catalyst into a solvent and controlling the temperature and time to completely reduce nitro groups. The solvent can be one of methanol, ethanol, isopropanol or DMF, the catalyst is one of nickel, cobalt, platinum and palladium noble metals, and the catalytic reduction only reduces nitro groups, so that the selectivity is high, the reduction rate is high, almost 100 percent of reduction is realized, the yield is high (more than 95 percent), the wastewater amount is less than 5 percent, the problems of incomplete reduction and low yield of the prior method are solved, and the method is suitable for industrial production. The purity of the 1, 8-diaminonaphthalene prepared by the method is up to more than 99%, the reduction rate of the raw material is high, almost 100% reduction is realized, the yield is higher than 95%, and the generated wastewater is less than 5% of the total yield.
Description
Technical Field
The invention relates to a method for synthesizing 1, 8-diaminonaphthalene by selective reduction of 1, 8-dinitronaphthalene.
Background
1, 8-diaminonaphthalene is an important dye intermediate, with grayish-red to gray or dark-brown needle crystals of the formula C10H10N2CAS number: 479-27-6, molecular weight 158.1998, 1, 8-diaminonaphthalene is an important intermediate for preparing oil-soluble pigment, has annual output of over ten thousand tons, and is mainly used for synthesizing solvent orange 60 and solvent red 135, which are widely used for coloring polystyrene, organic glass, rigid polyvinyl chloride and ABS.
CN: 1100403A discloses a process for preparing 1, 5-diaminonaphthalene and 1, 8-diaminonaphthalene by mixing dinitronaphthalene, iron powder, alcohol, water, glacial acetic acid, caustic soda and sodium bisulfite in a certain proportion, stirring, heating, keeping warm, diluting, precipitating, filtering and drying, which has serious environmental pollution and is a useless process route in the near future for the clear text of the state.
101823968 discloses a method for preparing 1, 8-diaminonaphthalene by reducing 1, 8-dinitronaphthalene with hydrazine hydrate, but the catalyst has the advantages of low activity, low selectivity, low yield and high cost, and is suitable for reducing short-line aromatic hydrocarbon.
CN: 101187031A adopts dilute sulfuric acid solution as electrolyte, and 1, 8-dinitronaphthalene is electrolytically reduced under the drive of constant potential through four steps of equipment preparation, electrolyte preparation, electrolysis and post-treatment, and the yield is 36.2-75.5%. It is difficult to use in industrial production due to the low yield.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects that the reduction rate is lower than 80 percent and the yield is lower than 70 percent in the production of 1, 8-dinitronaphthalene in the prior art, and provides a method for synthesizing 1, 8-diaminonaphthalene by selective reduction of 1, 8-dinitronaphthalene, which can improve the reduction rate and the yield.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for synthesizing 1, 8-diaminonaphthalene by selective reduction of 1, 8-dinitronaphthalene comprises the following steps:
s1, sequentially adding 1, 8-dinitronaphthalene, a solvent and a catalyst into a hydrogenation high-pressure kettle, replacing air in the kettle, adding hydrogen after replacement, keeping the pressure in the kettle at 1.5-3MPa, starting stirring, heating to 55-75 ℃ in the kettle, preserving heat for reaction, and finishing the reaction;
s2, taking out the reaction liquid in the S1, performing suction filtration on the reaction liquid, and filtering out the catalyst;
s3, distilling the filtrate of S2 under reduced pressure, evaporating the solvent and recovering the solvent;
and S4, cooling and crystallizing to obtain the 1, 8-diaminonaphthalene solid.
Further, the catalyst used in S1 is any one of nickel, cobalt, platinum, palladium or Pd. These catalysts can lower the activation energy and facilitate the breaking of old bonds and the formation of new bonds. These metals may be used as a catalyst, may be adsorbed on C, or may be used as an active adsorbent, or may be ionic.
Further, the solvent used in S1 is any one of methanol, ethanol, isopropanol or DMF. Ethanol or isopropanol is preferred.
Further, the heat preservation time is 4-12 hours.
Furthermore, the amount of solvent used in S1 is 8-12 times the mass of 1, 8-dinitronaphthalene.
Further, the distillation temperature in S3 is 45-55 ℃.
Further, the crystallization temperature in S4 is below-10 ℃.
On the other hand, the selection of the catalyst is closely related to the solvent of the reaction, the magnitude of the pressure, the temperature of the reaction and the time, and the adjustment of one catalyst can generate great difference, so that the results have great difference, and the ideal yield can not be obtained by simple experiments.
The invention has the following beneficial effects: the invention discloses a method for preparing 1, 8-diaminonaphthalene by selective reduction of 1, 8-dinitronaphthalene, which is a method for only generating 1, 8-diaminonaphthalene by adding a catalyst into a solvent and controlling the temperature and time to completely reduce nitro groups. The solvent can be one of methanol, ethanol, isopropanol or DMF, the catalyst is one of nickel, cobalt, platinum and palladium noble metals, and the catalytic reduction only reduces nitro groups, so that the selectivity is high, the reduction rate is high, almost 100 percent of reduction is realized, the yield is high (more than 95 percent), the wastewater amount is less than 5 percent, the problems of incomplete reduction and low yield of the prior method are solved, and the method is suitable for industrial production. The purity of the 1, 8-diaminonaphthalene prepared by the method is up to more than 99%, the reduction rate of the raw material is high, the raw material can be reduced by 100%, the impurities are few, the boiling point of the solvent is low, the distillation is easy, the yield is high, the yield is up to more than 95%, and the generated waste water is little and less than 5% of the total amount.
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
The first step is as follows: taking 30g of 1, 8-dinitronaphthalene and 300g of ethanol, adopting Pd as a catalyst, adsorbing the Pd on C to prepare Pd/C, wherein the addition amount of the Pd/C is 1.7g, and the mass percent of the Pd is about 5%, so that the catalyst has a good catalytic effect and is low in price; adding the mixture into a high-pressure reaction kettle, sealing the reaction kettle, replacing the air in the kettle with nitrogen for about 3 times, and replacing the nitrogen with hydrogen for about 3 times;
the second step is that: heating the temperature in the kettle to 65 ℃, and keeping the temperature for 6 hours, wherein the pressure is controlled to be 1.5 MPa;
the third step: after the reaction is finished, taking out reaction liquid, filtering out the catalyst, distilling out the solvent under reduced pressure, cooling to below-10 ℃, crystallizing and filtering out 20.6g of the product 1, 8-diaminonaphthalene. The purity of the product is over 97.2 percent and the yield is 94.7 percent.
Example 2
The first step is as follows: adding 80g of 1, 8-dinitronaphthalene, 300g of isopropanol and 4.8g of Pd/C into a high-pressure reaction kettle, sealing the reaction kettle, replacing the air in the kettle with nitrogen for about 3 times, and replacing the nitrogen with hydrogen for about 3 times;
the second step is that: heating the temperature in the kettle to 65 ℃, and keeping the temperature for 4 hours, wherein the pressure is controlled to be 1.5 MPa;
the third step: after the reaction is finished, taking out reaction liquid, filtering out the catalyst, distilling out the solvent under reduced pressure, cooling to the temperature of below-10 ℃, crystallizing and filtering out 55.8g of the product 1, 8-diaminonaphthalene, and detecting that the product purity is more than 98.3 percent and the yield is 96.2 percent.
Example 3
Adding 30g of 1, 8-dinitronaphthalene, 300g of ethanol and 1.8g of Pd/C into a high-pressure reaction kettle, sealing the reaction kettle, replacing the air in the kettle with nitrogen for about 3 times, and replacing the nitrogen with hydrogen for about 3 times;
the second step is that: heating the temperature in the kettle to 70 ℃, and keeping the temperature for 10 hours, wherein the pressure is controlled to be 2 MPa;
the third step: after the reaction is finished, taking out reaction liquid, filtering out the catalyst, distilling out the solvent under reduced pressure, cooling to below-10 ℃, crystallizing and filtering out 21.2g of the product 1, 8-diaminonaphthalene with the purity of 99.1 percent and the yield of 97.7 percent.
Example 4
The first step is as follows: adding 80g of 1, 8-dinitronaphthalene, 300g of isopropanol and Pd/C4.8g into a high-pressure reaction kettle, sealing the reaction kettle, replacing the air in the kettle with nitrogen for about 3 times, and replacing the nitrogen with hydrogen for about 3 times;
the second step is that: heating the temperature in the kettle to 70 ℃, and keeping the temperature for 6 hours, wherein the pressure is controlled to be 2 MPa;
the third step: after the reaction is finished, taking out reaction liquid, filtering out the catalyst, distilling out the solvent under reduced pressure, cooling to the temperature of below-10 ℃, crystallizing and filtering out 57.1g of the product 1, 8-diaminonaphthalene, and detecting that the product purity is 99.4 percent and the yield is 98.5 percent.
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 (7)
1. A method for synthesizing 1, 8-diaminonaphthalene by selective reduction of 1, 8-dinitronaphthalene is characterized by comprising the following steps:
s1, sequentially adding 1, 8-dinitronaphthalene, a solvent and a catalyst into a hydrogenation high-pressure kettle, replacing air in the kettle, adding hydrogen after replacement, keeping the pressure in the kettle at 1.5-3MPa, starting stirring, heating to 55-75 ℃ in the kettle, preserving heat for reaction, and finishing the reaction;
s2, taking out the reaction liquid in the S1, performing suction filtration on the reaction liquid, and filtering out the catalyst;
s3, distilling the filtrate of S2 under reduced pressure, evaporating the solvent and recovering the solvent;
and S4, cooling and crystallizing to obtain the 1, 8-diaminonaphthalene solid.
2. The method for selective reduction of 1, 8-dinitronaphthalene to 1, 8-diaminonaphthalene according to claim 1, wherein the catalyst used in S1 is any one of nickel, cobalt, platinum, palladium or Pd.
3. The method for selective reduction of 1, 8-dinitronaphthalene to 1, 8-diaminonaphthalene according to claim 1, wherein the solvent used in S1 is any one of methanol, ethanol, isopropanol or DMF.
4. The method for selective reduction of 1, 8-dinitronaphthalene to 1, 8-diaminonaphthalene according to claim 1, wherein the holding time in S1 is 4 to 12 hours.
5. The method for the selective reduction synthesis of 1, 8-diaminonaphthalene according to claim 1, 8-dinitronaphthalene, wherein the mass of the solvent used in S1 is 8 to 12 times the mass of 1, 8-dinitronaphthalene.
6. The method for the selective reduction of 1, 8-dinitronaphthalene to 1, 8-diaminonaphthalene according to claim 1, wherein the distillation temperature in S3 is 45-55 ℃.
7. The method for the selective reduction of 1, 8-dinitronaphthalene to 1, 8-diaminonaphthalene according to claim 1, wherein the crystallization temperature in S4 is below-10 ℃.
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| CN201911327020.9A CN111116378A (en) | 2019-12-20 | 2019-12-20 | Method for synthesizing 1, 8-diaminonaphthalene by selective reduction of 1, 8-dinitronaphthalene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115448868A (en) * | 2022-07-25 | 2022-12-09 | 青海黄河上游水电开发有限责任公司西宁太阳能电力分公司 | Method for strengthening catalytic hydrogenation reaction of nitro compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4026944A (en) * | 1974-08-10 | 1977-05-31 | Bayer Aktiengesellschaft | Process for manufacturing diaminonaphthalene |
| CN101575295A (en) * | 2009-05-20 | 2009-11-11 | 江苏工业学院 | Method for preparing diaminonaphthalene by catalytic hydrogenation of dinitronaphthalene |
| CN102924298A (en) * | 2012-11-15 | 2013-02-13 | 泰莱斯（南通）医药化工有限公司 | Separation method of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene |
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2019
- 2019-12-20 CN CN201911327020.9A patent/CN111116378A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4026944A (en) * | 1974-08-10 | 1977-05-31 | Bayer Aktiengesellschaft | Process for manufacturing diaminonaphthalene |
| CN101575295A (en) * | 2009-05-20 | 2009-11-11 | 江苏工业学院 | Method for preparing diaminonaphthalene by catalytic hydrogenation of dinitronaphthalene |
| CN102924298A (en) * | 2012-11-15 | 2013-02-13 | 泰莱斯（南通）医药化工有限公司 | Separation method of 1,5-diaminonaphthalene and 1,8-diaminonaphthalene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115448868A (en) * | 2022-07-25 | 2022-12-09 | 青海黄河上游水电开发有限责任公司西宁太阳能电力分公司 | Method for strengthening catalytic hydrogenation reaction of nitro compound |
| CN115448868B (en) * | 2022-07-25 | 2024-01-26 | 青海黄河上游水电开发有限责任公司西宁太阳能电力分公司 | Method for strengthening catalytic hydrogenation reaction of nitro compound |
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Effective date of registration: 20220303 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. |
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Application publication date: 20200508 |