CN1398857A - Synthesis of benzoxazolinone - Google Patents
Synthesis of benzoxazolinone Download PDFInfo
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- CN1398857A CN1398857A CN 02127421 CN02127421A CN1398857A CN 1398857 A CN1398857 A CN 1398857A CN 02127421 CN02127421 CN 02127421 CN 02127421 A CN02127421 A CN 02127421A CN 1398857 A CN1398857 A CN 1398857A
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Abstract
A synthesis process of benzoxazolinone is a reaction process is organic solvent in a sealed high pressure reactor with CO and o-nitrophhenol as raw material, Se as catalyst, DBU and triethylamine as cocatalyst. The molar amount of Se is 0.1-20 % that of reactant, organic strong alkali DBU 10-200 %, triethylamine 10-200%, the molar ratio of reactant to the solvent is 1 to 1-50, the reaction time is 2-20 hr, the reaction temperature is 50-200 deg.C and CO reactant pressure is 1-10 MPa gauge pressure. The present invention has simple operation, easy-to-obtain material, fewer reaction steps and high yield.
Description
Technical field
The present invention relates to the synthetic of a kind of benzoxazolinone compound, relate in particular to the method that a kind of catalysis of carbonyl is combined to benzoxazole quinoline compound.
Background technology
The benzoxazole quinoline is a kind of important fine chemicals.Can be used as the mildew-resistant of macromolecular material, anti-microbial inoculum, the mould inhibitor of cereal.The method of conventional synthetic Ben Bing oxazoline Tong Tong mainly adopts phosgenation or class phosgenation at present.Its weak point is that phosgene has severe toxicity, produces the big chloride by-product of macro-corrosion in the reaction process, severe corrosion equipment not only, also easy contaminate environment.Conventional synthetic benzene of while and Evil azoles quinoline Tong mainly adopt two to go on foot the method for walking, and promptly aromatic nitro compound reacts and the preparation benzoxazolinone with phosgene or phosgene substituent then earlier by being reduced into aromatic amino compound.The obvious complex operation of this method.Total recovery is also not too high.
Summary of the invention
The method that the object of the present invention is to provide a kind of reaction conditions gentleness, catalysis of carbonyl that cost is low to be combined to the benzoxazolinone compound.
For achieving the above object, technical scheme of the present invention is as follows: in the presence of carbon monoxide (CO), o-NP is a raw material, is catalyzer with selenium, and organic alkali is a promotor, heats in the autoclave of sealing in organic solvent and reacts; Reaction formula is as follows:
Wherein: the mole dosage of catalyzer is the 0.1-20% of reaction substrate.Promotor is 1, one or more of 8-diaza-bicyclo (5.4.0)-11 carbon seven alkene (DBU), triethylene diamine, triethylamine and TERTIARY BUTYL AMINE, and its mole dosage is the 10-200% of reaction substrate.
The mol ratio of reaction substrate and organic solvent is 1: 20-1: 200, preferred 1: 1-1: 50; Organic solvent adopts polarity or non-polar solvent, and polar solvent is toluene, tetrahydrofuran (THF) or chloroform, and non-polar solvent is normal hexane or benzene.
Reaction times is 2-20 hour.
Temperature of reaction is 50-200 ℃.
The CO reaction pressure is gauge pressure 1-10Mpa.
Wherein said CO can be the industrial tail gas that contains CO, and wherein the content sum of air, nitrogen, carbonic acid gas and/or water vapor equals 10% of cumulative volume.
The present invention has following advantage:
1, cost is low.Catalyzer is inexpensive, and investment goods is few, easily operation.
2, reaction conditions gentleness.Do not use deleterious phosgene, the three wastes are few, production easy to clean.
3, catalyzer is recyclable.Selenium powder is recyclable after the reaction uses again.
Specific implementation method
Below by embodiment in detail the present invention is described in detail; But the present invention is not limited to following embodiment.
Embodiment 1
In the stainless steel autoclave of 70ml, add o-NP (10mmol), Se (0.5mmol), DBU (10mmol), triethylamine (20mmol) and toluene 10ml, with after the CO displacement three times CO pressure is risen to 3MPa, put it in 160 ℃ the oil bath pan stirring reaction 3 hours, be chilled to room temperature, reaction solution concentrates, and column chromatography, elutriant are sherwood oil: ethyl acetate (5: 3), concentrate eluant gets product, and yield is 44.4%.137-138 ℃ of fusing point (mp).
Embodiment 2
In the stainless steel autoclave of 70ml, add o-NP (10mmol), Se (0.5mmol), DBU (10mmol), triethylamine (20mmol) and toluene 10ml, with after the CO displacement three times CO pressure is risen to 3MPa, put it in 160 ℃ the oil bath pan stirring reaction 5 hours, be chilled to room temperature, reaction solution concentrates, and column chromatography, elutriant are sherwood oil: ethyl acetate (5: 3), concentrate eluant gets product, and yield is 51.8%.mp137-138℃。
Embodiment 3
In the stainless steel autoclave of 70ml, add o-NP (10mmol), Se (0.5mmol), DBU (10mmol), triethylamine (20mmol) and toluene 10ml, with after the CO displacement three times CO pressure is risen to 3MPa, put it in 160 ℃ the oil bath pan stirring reaction 7 hours, be chilled to room temperature, reaction solution concentrates, and column chromatography, elutriant are sherwood oil: ethyl acetate (5: 3), concentrate eluant gets product, and yield is 66.7%.mp137-138℃。
Embodiment 4
In the stainless steel autoclave of 70ml, add o-NP (10mmol), Se (0.5mmol), DBU (10mmol), triethylamine (20mmol) and toluene 10ml, with after the CO displacement three times CO pressure is risen to 3MPa, put it in 160 ℃ the oil bath pan stirring reaction 9 hours, be chilled to room temperature, reaction solution concentrates, and column chromatography, elutriant are sherwood oil: ethyl acetate (5: 3), concentrate eluant gets product, and yield is 48.2%.mp137-138℃。
Embodiment 5
In the stainless steel autoclave of 70ml, add o-NP (10mmol), Se (0.5mmol), DBU (10mmol), triethylamine (20mmol) and toluene 10ml, with after the CO displacement three times CO pressure is risen to 3MPa, put it in 150 ℃ the oil bath pan stirring reaction 7 hours, be chilled to room temperature, reaction solution concentrates, and column chromatography, elutriant are sherwood oil: ethyl acetate (5: 3), concentrate eluant gets product, and yield is 52.0%.mp137-138℃。
Embodiment 6
In the stainless steel autoclave of 70ml, add o-NP (10mmol), Se (0.5mmol), DBU (10mmol), triethylamine (20mmol) and tetrahydrofuran (THF) (THF) 10ml, with after the CO displacement three times CO pressure is risen to 3MPa, put it in 160 ℃ the oil bath pan stirring reaction 7 hours, be chilled to room temperature, reaction solution concentrates, and column chromatography, elutriant are sherwood oil: ethyl acetate (5: 3), concentrate eluant gets product, and yield is 44.4%.mp137-138℃。
Embodiment 7
In the stainless steel autoclave of 70ml, add o-NP (10mmol), Se (0.5mmol), DBU (10mmol), triethylamine (20mmol) and 1,4-dioxane 10ml, with after the CO displacement three times CO pressure is risen to 3MPa, put it in 160 ℃ the oil bath pan stirring reaction 7 hours, and be chilled to room temperature, reaction solution concentrates, column chromatography, elutriant is a sherwood oil: ethyl acetate (5: 3), and concentrate eluant gets product, and yield is 40.0%.mp137-138℃。
Embodiment 8
In the stainless steel autoclave of 70ml, add o-NP (10mmol), Se (0.5mmol), DABCO (10mmol), triethylamine (20mmol) and toluene 10ml, with after the CO displacement three times CO pressure is risen to 3MPa, put it in 160 ℃ the oil bath pan stirring reaction 7 hours, be chilled to room temperature, reaction solution concentrates, and column chromatography, elutriant are sherwood oil: ethyl acetate (5: 3), concentrate eluant gets product, and yield is 54.8%.mp137-138℃。
Embodiment 9
In the stainless steel autoclave of 70ml, add o-NP (10mmol), Se (0.5mmol), DBU (10mmol) and toluene 10ml, with after the CO displacement three times CO pressure is risen to 3MPa, put it in 160 ℃ the oil bath pan stirring reaction 7 hours, be chilled to room temperature, reaction solution concentrates, and column chromatography, elutriant are sherwood oil: ethyl acetate (5: 3), concentrate eluant gets product, and yield is 57.0%.mp137-138℃。
Embodiment 10
In the stainless steel autoclave of 70ml, add o-NP (10mmol), Se (0.5mmol), triethylamine (20mmol) and toluene 10ml, with after the CO displacement three times CO pressure is risen to 3MPa, put it in 160 ℃ the oil bath pan stirring reaction 7 hours, be chilled to room temperature, reaction solution concentrates, and column chromatography, elutriant are sherwood oil: ethyl acetate (5: 3), concentrate eluant gets product, and yield is 44.4%.mp137-138℃。
Claims (7)
1, a kind of synthetic method of benzoxazolinone, o-NP is a raw material in the presence of carbon monoxide, is catalyzer with selenium, organic bases is a promotor, the reaction of in organic solvent, in enclosed autoclave, heating, reaction formula is as follows:
2, the method for claim 1, wherein:
The molar weight of catalyzer is the 0.1-20% of substrate;
The molar weight of promotor is the 10-200% of substrate;
The mol ratio of reaction substrate and organic solvent is 1: 20-1: 200
Reaction times is 2-20 hour;
Temperature of reaction is 50-200 ℃;
Reaction of carbon monoxide pressure is gauge pressure 1-10Mpa.
3, by claim 1 or 2 described methods, it is characterized in that described promotor is 1, one or more of 8-diaza-bicyclo (5.4.0)-11 carbon seven alkene, triethylene diamine, triethylamine and TERTIARY BUTYL AMINE.
4, by claim 1 or 2 described methods, it is characterized in that described carbon monoxide is industrial carbon monoxide tail gas, wherein the content sum of air, nitrogen, carbonic acid gas and/or water vapor equals 10% of cumulative volume.
5, by claim 1 or 2 described methods, it is characterized in that described organic solvent is one or more polarity or nonpolar inert solvent.
6, by claim 1,2 or 5 described methods, it is characterized in that described organic solvent is toluene, chloroform or tetrahydrofuran (THF); Non-polar solvent is hexane or benzene.
7, by claim 1 or 2 described methods, it is characterized in that the mol ratio of described reaction substrate and organic solvent is 1: 1-1: 50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02127421 CN1398857A (en) | 2002-07-31 | 2002-07-31 | Synthesis of benzoxazolinone |
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| CN 02127421 CN1398857A (en) | 2002-07-31 | 2002-07-31 | Synthesis of benzoxazolinone |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319954C (en) * | 2004-06-30 | 2007-06-06 | 中国科学院大连化学物理研究所 | Process for synthesizing benzoxazolinone compounds |
| CN101293875B (en) * | 2007-04-25 | 2011-05-11 | 中国科学院大连化学物理研究所 | Method for synthesizing oxazoline-2-ketone |
| CN109181483A (en) * | 2018-09-05 | 2019-01-11 | 安徽泰达新材料股份有限公司 | A kind of epoxy powder coating dulling and curing agent and the preparation method and application thereof |
| CN110698421A (en) * | 2019-12-16 | 2020-01-17 | 湖南速博生物技术有限公司 | Synthesis method of benzoxazolone |
-
2002
- 2002-07-31 CN CN 02127421 patent/CN1398857A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319954C (en) * | 2004-06-30 | 2007-06-06 | 中国科学院大连化学物理研究所 | Process for synthesizing benzoxazolinone compounds |
| CN101293875B (en) * | 2007-04-25 | 2011-05-11 | 中国科学院大连化学物理研究所 | Method for synthesizing oxazoline-2-ketone |
| CN109181483A (en) * | 2018-09-05 | 2019-01-11 | 安徽泰达新材料股份有限公司 | A kind of epoxy powder coating dulling and curing agent and the preparation method and application thereof |
| CN110698421A (en) * | 2019-12-16 | 2020-01-17 | 湖南速博生物技术有限公司 | Synthesis method of benzoxazolone |
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