CN109748877A - A kind of preparation method of 5-acetoacetamido benzimidazolone - Google Patents
A kind of preparation method of 5-acetoacetamido benzimidazolone Download PDFInfo
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- CN109748877A CN109748877A CN201910216884.7A CN201910216884A CN109748877A CN 109748877 A CN109748877 A CN 109748877A CN 201910216884 A CN201910216884 A CN 201910216884A CN 109748877 A CN109748877 A CN 109748877A
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Abstract
The present invention provides a kind of preparation methods of 5-acetoacetamido benzimidazolone, comprising the following steps: (1) is passed through sulfur dioxide gas in the water of Xiang Hanyou 5-Amino-2-benzimidazolinone；(2) ketene dimer and liquid alkaline is added dropwise simultaneously into system, reaction obtains 5-acetoacetamido benzimidazolone.Sulfur dioxide gas is used in preparation method provided by the invention, instead of acid common in current technique and antioxidant, is reduced costs, is avoided the generation of phosphorus-containing wastewater, product purity is high, high income, and the reaction time is short.
Description
Technical field
The invention belongs to Technology of Fine Chemical Industry technical fields, and in particular to a kind of 5-acetoacetamido benzimidazolone
Preparation method.
Background technique
5-acetoacetamido benzimidazolone (AABI) is a kind of important chemical intermediate, and series of products are extensive
Be applied to the fields such as medicine, pesticide, special material, and using it as coupling component preparation the organic face of benzimidazole ketone
Material has the excellent performances such as preferable heat-resisting, fast light, weatherability, solvent resistant, makes its huge market demand.
Acylation reaction system mainly occurs using 5-Amino-2-benzimidazolinone and ketene dimer as raw material in existing preparation method
Standby 5-acetoacetamido benzimidazolone.5-Amino-2-benzimidazolinone is easily oxidized as important source material, amino, in water
Solubility is low, and the solubility of 5-Amino-2-benzimidazolinone can be improved in acid condition, therefore existing processes are in acid condition mostly
Lower dissolution 5-Amino-2-benzimidazolinone, while antioxidant is added to avoid the oxidation of amino, currently used acid has phosphoric acid, sulphur
Acid, hydrochloric acid etc..Chinese patent CN 101307023A discloses one kind with 5-Amino-2-benzimidazolinone and ketene dimer, phosphoric acid, liquid
The method of alkali, water preparation 5-acetoacetamido benzimidazolone, the 5-acetoacetamido benzimidazolone of technique production
Although product purity is higher, total recovery only 75%, there is still very big room for promotion, the additions of concentrated phosphoric acid, so that producing
A large amount of phosphorus-containing wastewaters are produced in journey, are increased later period environmental protection treatment cost, are unfavorable for the popularization of green chemical concept；Acetylation
Heat preservation is up to 3 ~ 4 hours in the process, increases energy consumption.It is urged in addition, Chinese patent CN 103664794A discloses one kind in acidity
Under agent catalysis, 5-Amino-2-benzimidazolinone and ketene dimer, alcohol, water reaction prepare 5-acetoacetamido benzimidazolone
Although the product yield of method, method preparation is increased to 85%, but the processing of acid-bearing wastewater and using and recycling for alcohols solvent
Increase production cost；Meanwhile remaining alcohols solvent also to later product dry when buried security risk.Therefore it solves existing
The problem of synthesizing 5-acetoacetamido benzimidazolone technique has protection environment, reduction production cost very heavy
The meaning wanted.
Summary of the invention
It is an object of the invention to develop a kind of preparation method of 5-acetoacetamido benzimidazolone, by being passed through two
Sulfur oxide gas provides acidic environment, protects amino, had not only avoided the use of antioxidant, but also realize the system of salt in waste water
One, environment is protected, production cost is reduced.Product yield is high, with high purity, and the reaction time is short.
The invention discloses a kind of preparation methods of 5-acetoacetamido benzimidazolone, include the following steps:
(1) sulfur dioxide gas is passed through in the water of Xiang Hanyou 5-Amino-2-benzimidazolinone, solid dissolves after heating；
(2) ketene dimer and liquid alkaline is added dropwise simultaneously into system, in a certain range, reaction obtains 5- acetoacetyl to control pH value
Aminobenzimidazole ketone.
Water described in above-mentioned steps and 5-Amino-2-benzimidazolinone molar ratio are (185 ~ 215): 1, preferably 207:1；It is excellent
The temperature that is passed through of the sulfur dioxide gas of choosing is 0 ~ 40 DEG C；The sulfur dioxide gas is with 5-Amino-2-benzimidazolinone molar ratio
(0.09 ~ 0.30): 1, preferably 0.21:1；The ketene dimer and 5-Amino-2-benzimidazolinone molar ratio are (1.06 ~ 1.51):
1, preferably 1.27:1；The liquid alkaline and 5-Amino-2-benzimidazolinone molar ratio are (0.38 ~ 0.45): 1, preferably 0.28:1；
The a certain range of pH value is 3 ~ 7, preferably 4 ~ 6；Preferred reaction temperature is 60 ~ 90 DEG C；Reaction time is 20 min.
Beneficial effects of the present invention:
The invention discloses a kind of preparation methods of 5-acetoacetamido benzimidazolone, compared with the conventional method, the present invention
Using sulfur dioxide gas, plays the role of accelerating the dissolution of 5-Amino-2-benzimidazolinone and prevent oxidation, avoid simultaneously
The use of phosphoric acid reduces the amount of phosphorus-containing wastewater, realizes the unification of salt in waste water, is conducive to the protection of environment, is with water
Solvent reduces cost of the alcohols as solvent when, avoids security risk when product drying.Reacting maximum temperature is 90
DEG C, easy to operate and safe, products obtained therefrom purity >=99.5%, yield >=92%.
Specific embodiment
The specific embodiment of preparation method provided by the present invention is as follows, to further describe technical solution of the present invention,
But protection scope of the present invention is not limited to these examples.It is all equal without departing substantially from the change of present inventive concept or equivalent replacement
Including within protection scope of the present invention.
Embodiment 1:
At room temperature to equipped with 275 g water are added in blender four-hole bottle, 11 g 5-Amino-2-benzimidazolinones are started stirring, are passed through
0.99 g sulfur dioxide gas is warming up to 83 DEG C or so, and solid all dissolves, and 7.92 g ketene dimers are added dropwise simultaneously into system
With 2.75 g liquid alkaline, pH is controlled 4 ~ 6, is added dropwise, and product 5-acetoacetamido benzimidazolone is slowly precipitated, heat preservation
20 min are cooled to 50 DEG C hereinafter, filtering, drying, obtain 16.05 g (yield of brilliant white 5-acetoacetamido benzimidazolone
93.31%, purity 99.67%), 2 ~ 2.5 h of total time-consuming.
Embodiment 2:
Under environment same as Example 1,275 g water, 11 g 5- amino benzos are added into the four-hole bottle equipped with blender
Imidazolone starts stirring, and persistently overheating only dissolves a little solid to 90 DEG C, and 7.92 g ketene dimers are added dropwise simultaneously into system
With 2.75 g liquid alkaline, pH is controlled 4 ~ 6, is added dropwise, and product 5-acetoacetamido benzimidazolone is slowly precipitated, heat preservation
20 min are cooled to 50 DEG C hereinafter, filtering, drying, obtain 13.20 g (yield of brownish red 5-acetoacetamido benzimidazolone
76.74%, purity 65.37%), 2 ~ 2.5 h of total time-consuming contains big content of starting materials in products obtained therefrom, and appearance, yield and purity are not met
Similar products at home and abroad index.
Embodiment 3:
Under environment same as Example 1,350 g water, 15 g 5- amino benzos are added into the four-hole bottle equipped with blender
Imidazolone starts stirring, is passed through 2.5 g sulfur dioxide gas, is warming up to 62 DEG C or so solids and all dissolves, simultaneously into system
10.7 g ketene dimers and 2.8 g liquid alkaline are added dropwise, are added dropwise, product 5-acetoacetamido benzimidazolone i.e. slowly analysis
Out, 20 min are kept the temperature, are cooled to 50 DEG C hereinafter, filtering, drying, obtain brilliant white 5-acetoacetamido benzimidazolone 18.63
G(yield 79.45%, purity 99.23%), 2 ~ 2.5 h of total time-consuming is passed through any excess sulfur dioxide gas, though make 5- amino benzo miaow
Oxazolone dissolves in advance, but accordingly consumes a large amount of liquid alkaline, when liquid alkaline quality is inadequate, product yield and purity is caused to decline.
Embodiment 4:
Under environment same as Example 1,590 g water, 23 g 5- amino benzos are added into the four-hole bottle equipped with blender
Imidazolone starts stirring, is passed through 2.61 g sulfur dioxide gas, is warming up to 85 DEG C or so, and solid all dissolves, same into system
When be added dropwise 23 g ketene dimers and 5.75 g liquid alkaline, pH is controlled 4 ~ 6, is added dropwise, product 5- acetyl acetamide benzo miaow
Oxazolone is slowly precipitated, and keeps the temperature 20 min, is cooled to 50 DEG C hereinafter, filtering, drying, obtain brilliant white 5- acetyl acetamide benzo
32.98 g of imidazolone (yield 91.71%, purity 99.23%), 2 ~ 2.5 h of total time-consuming, when ketene dimer excess, product yield
And purity slightly reduces, and increases production cost.
Claims (8)
1. a kind of preparation method of 5-acetoacetamido benzimidazolone, comprising the following steps:
(1) sulfur dioxide gas is passed through into the water containing 5-Amino-2-benzimidazolinone under certain temperature；
(2) ketene dimer and liquid alkaline is added dropwise simultaneously into step (1) system, pH value is controlled in a certain range, in certain temperature
Under react, after held for some time, obtain 5-acetoacetamido benzimidazolone.
2. preparation method according to claim 1, which is characterized in that the water is with 5-Amino-2-benzimidazolinone molar ratio
(185 ~ 215): 1.
3. preparation method according to claim 1, which is characterized in that certain temperature as described in step (1) is 0 ~ 40 DEG C.
4. preparation method according to claim 1, which is characterized in that the sulfur dioxide gas and 5- aminobenzimidazole
Ketone molar ratio is (0.09 ~ 0.30): 1.
5. preparation method according to claim 1, which is characterized in that the ketene dimer rubs with 5-Amino-2-benzimidazolinone
You are than being (1.06 ~ 1.51): 1.
6. preparation method according to claim 1, which is characterized in that the liquid alkaline and 5-Amino-2-benzimidazolinone molar ratio
For (0.38 ~ 0.45): 1.
7. preparation method according to claim 1, which is characterized in that a certain range of pH value described in step (2) is 3
~ 7, the certain temperature is 60 ~ 90 DEG C, and the certain time is 20 min.
8. preparation method according to claim 1, which is characterized in that the degree of the liquid alkaline is 30 ~ 32%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845424A (en) * | 2019-12-11 | 2020-02-28 | 山东汇海医药化工有限公司 | Preparation method of 5-acetoacetylaminobenzimidazolone |
| CN111039872A (en) * | 2019-12-11 | 2020-04-21 | 山东汇海医药化工有限公司 | Method for improving yield of 5-acetoacetylaminobenzimidazolone |
| CN111763174A (en) * | 2020-08-03 | 2020-10-13 | 山东汇海医药化工有限公司 | Method for reducing distillation residues of 5-acetoacetylaminobenzimidazolone mother liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110845424A (en) * | 2019-12-11 | 2020-02-28 | 山东汇海医药化工有限公司 | Preparation method of 5-acetoacetylaminobenzimidazolone |
| CN111039872A (en) * | 2019-12-11 | 2020-04-21 | 山东汇海医药化工有限公司 | Method for improving yield of 5-acetoacetylaminobenzimidazolone |
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| CN111763174A (en) * | 2020-08-03 | 2020-10-13 | 山东汇海医药化工有限公司 | Method for reducing distillation residues of 5-acetoacetylaminobenzimidazolone mother liquor |
| CN111763174B (en) * | 2020-08-03 | 2023-06-09 | 山东汇海医药化工有限公司 | Method for reducing distillation residues of 5-acetoacetyl amino benzimidazolone mother liquor |
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