CN117447405A - Energy-saving and environment-friendly method for preparing benzimidazolone - Google Patents
Energy-saving and environment-friendly method for preparing benzimidazolone Download PDFInfo
- Publication number
- CN117447405A CN117447405A CN202311445312.9A CN202311445312A CN117447405A CN 117447405 A CN117447405 A CN 117447405A CN 202311445312 A CN202311445312 A CN 202311445312A CN 117447405 A CN117447405 A CN 117447405A
- Authority
- CN
- China
- Prior art keywords
- benzimidazolone
- energy
- saving
- phenylenediamine
- urea
- 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.)
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- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004202 carbamide Substances 0.000 claims abstract description 27
- 238000006481 deamination reaction Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000006378 damage Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 208000027418 Wounds and injury Diseases 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 208000014674 injury Diseases 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000011343 solid material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 8
- 230000009615 deamination Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- KQNZKBRSEJLVEO-UHFFFAOYSA-N 3-oxo-n-(2-oxobenzimidazol-5-yl)butanamide Chemical compound C1=C(NC(=O)CC(=O)C)C=CC2=NC(=O)N=C21 KQNZKBRSEJLVEO-UHFFFAOYSA-N 0.000 description 1
- 150000008641 benzimidazolones Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000004987 o-phenylenediamines Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/26—Oxygen atoms
-
- 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
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention relates to the field of chemical intermediate preparation, and discloses an energy-saving and environment-friendly method for preparing benzimidazolone, which comprises the following steps of: urea and o-phenylenediamine in a molten state are adopted; urea and o-phenylenediamine in a molten state are conveyed through a pipeline and added into a benzimidazolone three-in-one reaction kettle; deamination reaction; preserving heat and cooling; crushing and discharging. The invention effectively utilizes the melting heat energy of urea and o-phenylenediamine in a melting state, reduces the energy waste and has good energy-saving effect; the operations of manually feeding solid materials, manually removing bags and the like are reduced, and good social benefits are achieved; the preparation process does not need any solvent participation, avoids human injury and pollutant generation caused by using the solvent, and has good safety and environmental protection benefits; the product yield is high, the purity is high, and the production requirement is met; reasonable process, simple and convenient operation and is beneficial to industrialized production and popularization.
Description
Technical Field
The invention relates to the field of chemical intermediate preparation, in particular to an energy-saving and environment-friendly method for preparing benzimidazolone.
Background
Benzimidazolone is an important organic intermediate, and is especially applied to the fields of medicines, pigments, pesticides and the like.
The literature reports the following methods:
in US-4138568, o-phenylenediamine compounds are reacted with urea and urea derivatives in a water-insoluble organic solvent at a temperature of 100 ℃ to 200 ℃ to obtain benzimidazolone, which is then subjected to a complicated purification process, and the solvent consumption is high, resulting in a large amount of waste liquid.
In the J.am.chem.Soc.80,1657 (1958) publication, a process for preparing benzimidazolone by reacting o-phenylenediamine with phosgene is provided. However, phosgene used in the method is highly dangerous, and hydrogen chloride which is a byproduct generated in the reaction is highly corrosive to equipment.
3. In DE2052026, water is used as reaction medium, o-phenylenediamine and urea are condensed, the yield can reach 96% under the condition of pressurization, and in the new synthesis method of 5-acetoacetylamino benzimidazolone in the journal of chemistry and bioengineering in China, 2003, a method for synthesizing benzimidazolone by reacting o-phenylenediamine and urea in water is disclosed. The method is carried out at 90-120 ℃ and pH is controlled to 4-9 by acid regulation, thus preparing benzimidazolone, the yield and the product quality are unstable due to unstable reaction, and a large amount of wastewater causes environmental pollution.
4. The current large-scale industrial production process is that solid o-phenylenediamine and urea are subjected to reflux deamination under chlorobenzene or other high-boiling point solvents, then the solvents are concentrated and recovered, then water or mother liquor of the previous batch is added, and the temperature is reduced and the materials are centrifugally thrown.
In summary, the existing methods for preparing benzimidazolones generally suffer from the following drawbacks:
the used organic solvent has great harm to human body, and the process is complicated with a large amount of waste liquid;
2. phosgene has high danger, and the reaction byproduct hydrogen chloride corrodes equipment seriously, so that the industrial production is not suitable;
3. the water is used as solvent for pressurization or acid regulation, the pressurization process has high risk, the yield is slightly low, the acid regulation generates a large amount of inorganic salt, the reaction is unstable, and the product yield and quality are unstable.
4. The o-phenylenediamine and the urea are all solids in a molten state, and the solid o-phenylenediamine and the urea obtained by cooling and crushing are further used for synthesizing benzimidazolone, so that the waste of the energy of the o-phenylenediamine and the urea in the molten state is caused.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides an energy-saving and environment-friendly method for preparing benzimidazolone, which has the following technical scheme:
an energy-saving and environment-friendly method for preparing benzimidazolone, which comprises the following steps:
(1) Preparing materials: adopting urea and o-phenylenediamine in a molten state to replace solid urea and o-phenylenediamine;
(2) Feeding: urea and o-phenylenediamine in a molten state are conveyed through a pipeline and added into a benzimidazolone three-in-one reaction kettle;
(3) Deamination reaction: heating a benzimidazolone three-in-one reaction kettle to perform deamination reaction to obtain a primary benzimidazolone product;
(4) And (3) heat preservation and temperature reduction: after the reaction is finished, continuing to keep the temperature, and then cooling;
(5) Crushing and discharging: starting the crushing function of the benzimidazolone three-in-one reaction kettle, and crushing and discharging to obtain a qualified benzimidazolone product.
Further, the molar ratio of urea to o-phenylenediamine in the step (2) is 1 (0.9-1.1).
Furthermore, the benzimidazolone three-in-one reaction kettle in the step (2) has the functions of reaction, crushing and drying.
Further, the temperature of the benzimidazolone three-in-one reaction kettle in the step (3) is raised to 128-137 ℃.
Further, the step (4) is kept at 130-132 ℃ for 2-5 hours.
Further, the temperature of the step (4) is reduced to 40-60 ℃.
Furthermore, the qualified product yield of the benzimidazolone obtained in the step (5) is 99.3-99.6%.
Furthermore, the purity of the qualified benzimidazolone product obtained in the step (5) is 99.4-99.7%.
The synthetic route of the invention is as follows:
compared with the prior art, the invention has the following beneficial technical effects:
1. the invention selects urea and o-phenylenediamine to react in a molten state to prepare the benzimidazolone, effectively utilizes the melting heat energy of the urea and the o-phenylenediamine in the molten state, reduces the energy waste and has good energy-saving effect.
2. The urea and the o-phenylenediamine in a molten state are conveyed to the benzimidazolone cyclization post through the pipeline, so that the operations of manually feeding solid materials, manually unpacking bags and the like are reduced, the workload is reduced, the labor intensity is reduced, and the method has good social benefits.
3. The preparation process of the invention does not need any solvent, avoids human injury and pollutant generation caused by using the solvent, and has good safety and environmental protection benefits.
4. The invention has qualified product quality and meets the production requirement. The product yield is up to 99.6% and the purity is up to 99.7% by measurement.
The invention has reasonable process and simple and convenient operation, and is beneficial to industrialized production and popularization.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the scope of the present invention is not limited to these examples. All changes and equivalents that do not depart from the gist of the invention are intended to be within the scope of the invention.
Example 1
Adding urea and o-phenylenediamine in a molten state into a three-in-one reaction kettle through a tank area according to the molar ratio of the urea to the o-phenylenediamine being 1:1.05; heating to 128-132 deg.c to perform deamination; after the reaction is finished, keeping the temperature at 130 ℃ for 2 hours, and then cooling to 50 ℃; and opening a solid discharge valve of the reaction kettle to obtain qualified benzimidazolone, wherein the yield of the benzimidazolone is 99.30% and the purity is 99.56%.
Example 2
Adding urea and o-phenylenediamine in a molten state into a three-in-one reaction kettle through a tank area according to the molar ratio of the urea to the o-phenylenediamine being 1:1.1; heating to 133-137 deg.c for deamination; after the reaction is finished, continuing to keep the temperature at 132 ℃ for 3 hours, and then cooling to 60 ℃; and opening a solid discharge valve of the reaction kettle to obtain qualified benzimidazolone, wherein the yield of the benzimidazolone is 99.40% and the purity is 99.36%.
Example 3
Adding urea and o-phenylenediamine in a molten state into a three-in-one reaction kettle through a tank area according to the molar ratio of the urea to the o-phenylenediamine being 1:0.9; heating to 128-132 deg.c to perform deamination; after the reaction is finished, keeping the temperature at 130 ℃ for 5 hours, and then cooling to 40 ℃; and opening a solid discharge valve of the reaction kettle to obtain qualified benzimidazolone, wherein the yield of the benzimidazolone is 99.60%, and the purity is 99.66%.
The technical sections of the present invention that are not described in detail are known in the art.
Claims (8)
1. An energy-saving and environment-friendly method for preparing benzimidazolone is characterized by comprising the following steps:
(1) Preparing materials: adopting urea and o-phenylenediamine in a molten state to replace solid urea and o-phenylenediamine;
(2) Feeding: urea and o-phenylenediamine in a molten state are conveyed through a pipeline and added into a benzimidazolone three-in-one reaction kettle;
(3) Deamination reaction: heating a benzimidazolone three-in-one reaction kettle to perform deamination reaction to obtain a primary benzimidazolone product;
(4) And (3) heat preservation and temperature reduction: after the reaction is finished, continuing to keep the temperature, and then cooling;
(5) Crushing and discharging: starting the crushing function of the benzimidazolone three-in-one reaction kettle, and crushing and discharging to obtain a qualified benzimidazolone product.
2. The method for preparing benzimidazolone in an energy-saving and environment-friendly manner according to claim 1, wherein the molar ratio of urea to o-phenylenediamine in the step (2) is 1 (0.9-1.1).
3. The method for preparing benzimidazolone in an energy-saving and environment-friendly manner according to claim 1, wherein the three-in-one reaction kettle of the benzimidazolone in the step (2) has the functions of reaction, crushing and drying.
4. The method for preparing benzimidazolone in an energy-saving and environment-friendly manner according to claim 1, wherein the temperature of the three-in-one benzimidazolone reaction kettle in the step (3) is raised to 128-137 ℃.
5. The method for preparing benzimidazolone in energy saving and environment friendly manner according to claim 1, wherein the continuous heat preservation in the step (4) is kept at 130-132 ℃ for 2-5 h.
6. The method for preparing benzimidazolone in energy saving and environment protection according to claim 1, wherein the temperature reduction in the step (4) is to reduce the temperature to 40-60 ℃.
7. The method for preparing benzimidazolone in an energy-saving and environment-friendly manner according to claim 1, wherein the yield of the qualified benzimidazolone product obtained in the step (5) is 99.3% -99.6%.
8. The method for preparing benzimidazolone in an energy-saving and environment-friendly manner according to claim 1, wherein the purity of the qualified benzimidazolone product obtained in the step (5) is 99.4% -99.7%.
Priority Applications (1)
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CN202311445312.9A CN117447405A (en) | 2023-11-02 | 2023-11-02 | Energy-saving and environment-friendly method for preparing benzimidazolone |
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CN202311445312.9A CN117447405A (en) | 2023-11-02 | 2023-11-02 | Energy-saving and environment-friendly method for preparing benzimidazolone |
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CN117447405A true CN117447405A (en) | 2024-01-26 |
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CN202311445312.9A Pending CN117447405A (en) | 2023-11-02 | 2023-11-02 | Energy-saving and environment-friendly method for preparing benzimidazolone |
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- 2023-11-02 CN CN202311445312.9A patent/CN117447405A/en active Pending
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