CN107935937A - A kind of method for preparing benzimidazolone - Google Patents
A kind of method for preparing benzimidazolone Download PDFInfo
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- CN107935937A CN107935937A CN201711336208.0A CN201711336208A CN107935937A CN 107935937 A CN107935937 A CN 107935937A CN 201711336208 A CN201711336208 A CN 201711336208A CN 107935937 A CN107935937 A CN 107935937A
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- reaction
- benzimidazolone
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- water
- phenylenediamine
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The present invention relates to a kind of method for preparing benzimidazolone, with urea in water and under alkaline condition, ring-closure reaction occurs for o-phenylenediamine；After reaction, partial solvent water is steamed, is down to room temperature afterwards, is filtered, dry benzimidazolone；Reaction mother liquor is applied mechanically.The present invention does cyclizing agent using urea, and the accessory substance of generation is easy to absorb, and does not produce waste water；Realize that reaction mass carries out in homogeneous reaction system, reaction mass is sufficiently mixed；Reaction temperature is constant, and reaction is easily controllable；Aqueous solvent time is used, and is realized green and is combined to, product yield reaches 99%, and purity reaches 99.0%.
Description
Technical field
The invention belongs to chemical intermediate preparation field, and in particular to a kind of method for preparing benzimidazolone.
Background technology
Benzimidazolone is important organic intermediate, is particularly applied to the fields such as medicine, pigment and pesticide.
J.Am.Chem.Soc.80, in document disclosed in 1657 (1958), there is provided one kind o-phenylenediamine and phosgene are anti-
The method that benzimidazolone should be prepared.But phosgene used in the method has the danger of height, the by-product of generation is in addition reacted
Thing hydrogen chloride has equipment very strong corrosivity.
In US-4138568, o-phenylenediamine class compound and urea and urea derivative are anti-in water-insoluble organic solvents
Should, wherein temperature obtains benzimidazolone at 100 DEG C to 200 DEG C, then to pass through complicated purification process, and solvent consumption is big,
Produce a large amount of waste liquids.
In DE2052026, using water as reaction medium, o-phenylenediamine and urea condensation, yield can under an increased pressure
Reach 96%.
US-4269989 and Chinese periodical《Chemistry and bioengineering》Supplementary issue 5- acetoacetyl amino benzo miaows in 2003
In the new synthetic method of oxazolone, a kind of method of o-phenylenediamine in water and urea reaction synthesizing benzimidazole ketone is disclosed.This
Method temperature, using sour adjustment control pH 4 to 9, prepares benzimidazolone at 90 DEG C to 120 DEG C, unstable due to reacting, and leads
Yield, unstable product quality are caused, and substantial amounts of waste water causes to pollute environment.
Sum up, the existing method for preparing benzimidazolone usually has the following disadvantages：
1st, phosgene has the danger of height, and byproduct of reaction hydrogen-chloride etching equipment is serious, unsuitable industrialized production；
2nd, the organic solvent used is big to human injury, and process complexity is with a large amount of waste liquids；
3rd, it is then pressurization or adjusts acid using water as solvent, pressing technology is dangerous big, and yield is lower slightly, adjusts acid to produce a large amount of nothings
Machine salt, and react unstable, product yield, quality are unstable.
The content of the invention
It is an object of the invention to provide a kind of simple process, in high yield, the method for preparing benzimidazolone of high-purity.
The technical solution adopted by the present invention to solve the technical problems is：A kind of method for preparing benzimidazolone, including
Following steps：
1) with urea under the conditions of solvent and addition alkaline conditioner ring-closure reaction occurs for o-phenylenediamine；
2) partial solvent after reaction, is steamed, is down to room temperature, is filtered, dry benzimidazolone；Accessory substance therein
Ammonia is absorbed with water, mother liquor and steam water jacket use.
Specifically, the mass ratio that feeds intake of the urea in the step 1) and o-phenylenediamine is 1.3-1.0：1.
Specifically, step 1) the neutral and alkali conditioning agent is the one or more in sodium hydroxide, hydrazine hydrate or sodium carbonate；
The mass ratio that feeds intake of alkaline conditioner and solvent is 0.02-0.07：1, pH is adjusted between 8-11.
Specifically, solvent is water in the step 1), and aqueous solvent and the o-phenylenediamine mass ratio that feeds intake are 1-3：1.
Specifically, the reaction temperature of ring-closure reaction is 100-110 DEG C in the step 1), when the reaction time is 4-10 small.
Specifically, the amount of solvent is steamed in the step 2) to feed intake for solvent the 30-70% of quality.
The chemical equation that benzimidazolone is prepared in the present invention is as follows：
The present invention selects urea to prepare benzimidazolone with o-phenylenediamine reaction, and cyclizing agent, the pair of generation are done using urea
Product is easy to absorb；Alkaline conditioner is added, the ammonia being dissolved in solvent can be effectively reduced, promotes reaction to carry out,
And can effectively suppress the oxidation of o-phenylenediamine in alkaline environment, side reaction is reduced, the mother liquor after reaction can be with circulating sleeve
With, without repeatedly addition alkaline conditioner, use less material, save Material Cost；Realize reaction mass in homogeneous reaction
Carried out in system, reaction mass is sufficiently mixed；Aqueous solvent time is used, and is realized green and is combined to, product yield is pure up to 99%
Degree is more than 99.0%.
Embodiment
It is the specific embodiment of the present invention below, technical scheme is described further, but the present invention
Protection domain is not limited to these embodiments.It is every to be included in the present invention without departing substantially from the change of present inventive concept or equivalent substitute
Protection domain within.
Embodiment 1
In the 1000ml three-necked flasks equipped with electric stirring, reflux condensing tube and thermometer, 100g urea, 100g are added
O-phenylenediamine, 200g water and 10g basic solvents, pH value 11, opens stirring and is continuously heating to 105 DEG C, reaction insulation reaction 4 is small
When.Reaction is finished, and is distilled out 100g water, is down to room temperature, is filtered, water washing, is dried to obtain white products, yield 99.6%, purity
99.5%.Recycling Mother Solution is applied mechanically, and applies mechanically the product yield obtained after 4 times and purity such as following table：
| Apply mechanically number | Yield (%) | Purity (%) |
| 1 | 99.5 | 99.4 |
| 2 | 99.2 | 99.5 |
| 3 | 99.3 | 99.3 |
| 4 | 99.4 | 99.1 |
As can be seen from the above table, purity and yield impact very little of the mother liquid recycle to product.Solvent repeatedly can directly cover
With.
Embodiment 2
In the 1000ml three-necked flasks equipped with electric stirring, reflux condensing tube and thermometer, 130g urea, 100g are added
O-phenylenediamine, 300g water and 6g basic solvents, pH value 9, opens stirring and is continuously heating to 110 DEG C, reaction insulation reaction 8 is small
When.Reaction is finished, and is distilled out 210g water, is down to room temperature, is filtered, water washing, is dried to obtain white products, yield 99.3%, purity
99.4%.
Embodiment 3
In the 1000ml three-necked flasks equipped with electric stirring, reflux condensing tube and thermometer, 120g urea, 100g are added
O-phenylenediamine, 100g water and 7g basic solvents, pH value 10, opens stirring and is continuously heating to 100 DEG C, reaction insulation reaction 10 is small
When.Reaction is finished, and is distilled out 30g water, is down to room temperature, is filtered, water washing, is dried to obtain white products, yield 99.2%, purity
99.5%.
Embodiment 4
In the 1000ml three-necked flasks equipped with electric stirring, reflux condensing tube and thermometer, 110g urea, 100g are added
O-phenylenediamine, 300g water and 9g basic solvents, pH value 8, opens stirring and is continuously heating to 102 DEG C, reaction insulation reaction 6 is small
When.Reaction is finished, and is distilled out 150g water, is down to room temperature, is filtered, water washing, is dried to obtain white products, yield 99.3%, purity
99.1%.
Claims (6)
- A kind of 1. method for preparing benzimidazolone, it is characterised in that comprise the following steps：1) with urea under the conditions of solvent and addition alkaline conditioner ring-closure reaction occurs for o-phenylenediamine；2) partial solvent after reaction, is steamed, is down to room temperature, is filtered, dry benzimidazolone；Accessory substance ammonia therein Absorbed with water, mother liquor and steam water jacket use.
- 2. the method as claimed in claim 1 for preparing benzimidazolone, it is characterised in that urea and neighbour in the step 1) The mass ratio that feeds intake of phenylenediamine is 1.3-1.0：1.
- 3. the method as claimed in claim 1 for preparing benzimidazolone, it is characterised in that step 1) the neutral and alkali conditioning agent For the one or more in sodium hydroxide, hydrazine hydrate or sodium carbonate；The mass ratio that feeds intake of alkaline conditioner and solvent is 0.02- 0.07：1, pH is adjusted between 8-11.
- 4. the method as claimed in claim 1 for preparing benzimidazolone, it is characterised in that solvent is water in the step 1), Aqueous solvent and the o-phenylenediamine mass ratio that feeds intake are 1-3：1.
- 5. the method as claimed in claim 1 for preparing benzimidazolone, it is characterised in that ring-closure reaction in the step 1) Reaction temperature is 100-110 DEG C, when the reaction time is 4-10 small.
- 6. the method as claimed in claim 1 for preparing benzimidazolone, it is characterised in that steam solvent in the step 2) Measure the 30-70% for the quality that feeds intake for solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711336208.0A CN107935937A (en) | 2017-12-14 | 2017-12-14 | A kind of method for preparing benzimidazolone |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711336208.0A CN107935937A (en) | 2017-12-14 | 2017-12-14 | A kind of method for preparing benzimidazolone |
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| CN107935937A true CN107935937A (en) | 2018-04-20 |
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| CN201711336208.0A Pending CN107935937A (en) | 2017-12-14 | 2017-12-14 | A kind of method for preparing benzimidazolone |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558888A (en) * | 2018-05-31 | 2018-09-21 | 兰州大学 | A kind of synthetic method of azophenlyene and imidazolone |
| CN109320462A (en) * | 2018-11-23 | 2019-02-12 | 山东汇海医药化工有限公司 | A kind of method of o-phenylenediamine impurity in reduction 5-Nitro-2-benzimidazolinone |
| CN111362879A (en) * | 2020-04-28 | 2020-07-03 | 山东汇海医药化工有限公司 | Method for preparing benzimidazolone in aqueous solvent |
| CN116003298A (en) * | 2022-12-23 | 2023-04-25 | 山东汇海医药化工有限公司 | Method for recovering urea from benzimidazolone synthesis reaction mother liquor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4269989A (en) * | 1978-12-21 | 1981-05-26 | Hoechst Aktiengesellschaft | Process for the preparation of benzimidazolone-(2) |
| CN101307023A (en) * | 2008-05-23 | 2008-11-19 | 东营市天正化工有限公司 | Production process of 5-acetyl acetamino benzimidazolone |
-
2017
- 2017-12-14 CN CN201711336208.0A patent/CN107935937A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4269989A (en) * | 1978-12-21 | 1981-05-26 | Hoechst Aktiengesellschaft | Process for the preparation of benzimidazolone-(2) |
| CN101307023A (en) * | 2008-05-23 | 2008-11-19 | 东营市天正化工有限公司 | Production process of 5-acetyl acetamino benzimidazolone |
Non-Patent Citations (1)
| Title |
|---|
| 姚光源等: "5-乙酰乙酰基氨基苯并咪唑酮的合成新工艺", 《化学与生物工程》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558888A (en) * | 2018-05-31 | 2018-09-21 | 兰州大学 | A kind of synthetic method of azophenlyene and imidazolone |
| CN109320462A (en) * | 2018-11-23 | 2019-02-12 | 山东汇海医药化工有限公司 | A kind of method of o-phenylenediamine impurity in reduction 5-Nitro-2-benzimidazolinone |
| CN111362879A (en) * | 2020-04-28 | 2020-07-03 | 山东汇海医药化工有限公司 | Method for preparing benzimidazolone in aqueous solvent |
| WO2021218073A1 (en) * | 2020-04-28 | 2021-11-04 | 山东汇海医药化工有限公司 | Method for preparing benzimidazolone in aqueous solvent |
| CN116003298A (en) * | 2022-12-23 | 2023-04-25 | 山东汇海医药化工有限公司 | Method for recovering urea from benzimidazolone synthesis reaction mother liquor |
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