CN103172588A - Preparation method for 1,2-benzo isothiazolinone - Google Patents
Preparation method for 1,2-benzo isothiazolinone Download PDFInfo
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- CN103172588A CN103172588A CN2013100952306A CN201310095230A CN103172588A CN 103172588 A CN103172588 A CN 103172588A CN 2013100952306 A CN2013100952306 A CN 2013100952306A CN 201310095230 A CN201310095230 A CN 201310095230A CN 103172588 A CN103172588 A CN 103172588A
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Abstract
The invention discloses a preparation method for 1,2-benzo isothiazolinone, which comprises the following steps of adding sodium sulphide and sulphur into water and reacting so as to prepare sodium disulfide solution; dissolving chlorobenzonitrile into organic solvent so as to prepare chlorobenzonitrile solution; adding a catalyst into the chlorobenzonitrile solution, then dropping the sodium disulfide solution for reaction, and standing for layering, wherein the oil phase product is double sulfo-cyanophenyl solution; and adding water into the double sulfo-cyanophenyl solution for cooling, then aerating oxidant for reacting, heating at the later stage of the reaction, and finally preparing the product of 1,2-benzo isothiazolinone. According to the preparation method for 1,2-benzo isothiazolinone, one the one hand, the production cost for 1,2-benzo isothiazolinone is lowered, on the other hand, the production environment is improved and the preparation method is beneficial to environment protection.
Description
Technical field
The invention belongs to field of fine chemical, relate in particular to a kind of 1, the preparation method of 2-BIT.
Background technology
1,2-BIT is a kind of wide spectrum, efficient industrial antimildew disinfectant, and it is widely used in paint field.Industrial manufacture process mainly contained two kinds in the past, and a kind of is take adjacent amido phenylformic acid as starting raw material, made two sulfo-water phenylformic acid, then made 1,2-BIT through chloride, chlorination, amination; Another kind is take o-chloro benzonitrile or o-chlorobenzaldehyde as starting raw material, after thiol reactant, reoxidizes cyclization and makes 1,2-BIT.Above first method raw material is somewhat expensive, operational path long, the industrial production cost compare is high, and second method is owing to will using the mercaptan raw material, due to the mercaptan foul smelling, therefore production environment is poor.
Summary of the invention
It is a kind of 1 that the technical problem to be solved in the present invention is to provide, and the preparation method of 2-BIT reduces the production cost of 1,2-BIT on the one hand; Improve on the other hand production environment, be beneficial to environmental protection.
For solving the problems of the technologies described above, the invention provides a kind ofly 1, the preparation method of 2-BIT comprises the following steps:
(1) sodium sulphite and sulphur are added to the water through reaction make sodium disulfide solution;
(2) o-chloro benzonitrile is dissolved in is made into o-chloro benzonitrile solution in organic solvent;
(3) add catalyzer in described o-chloro benzonitrile solution, splash into subsequently described sodium disulfide solution and react, standing demix after reaction, its oil-phase product is two sulfo-cyanophenyl solution; With
(4) with adding water and cooling in described pair of sulfo-cyanophenyl solution, pass into subsequently oxygenant and react, the reaction later stage heats up, and finally generates product 1, the 2-BIT.
As of the present invention a kind of 1, a kind of preferred version of the preparation method of 2-BIT, make sodium disulfide solution through reaction comprise wherein said sodium sulphite and sulphur be added to the water:
Sodium sulphite is added water be made into the aqueous solution that mass percent is 20%-50%;
Add equimolar sulphur, heated and stirred is reacted under 70-100 ℃, until the whole solvent solns of sulphur are transparent, finally makes sodium disulfide solution.
As of the present invention a kind of 1, a kind of preferred version of the preparation method of 2-BIT, wherein said o-chloro benzonitrile is dissolved in is made into o-chloro benzonitrile solution and comprises in organic solvent:
O-chloro benzonitrile is dissolved in organic solvent, and being made into mass percent is the o-chloro benzonitrile solution of 20%-70%, and described organic solvent is any one in toluene, chlorobenzene and ethylene dichloride.
As of the present invention a kind of 1, a kind of preferred version of the preparation method of 2-BIT, describedly add catalyzer in described o-chloro benzonitrile solution, drip subsequently described sodium disulfide solution and react, standing demix after reaction, its oil-phase product comprises for two sulfo-cyanophenyl solution:
Add catalyzer in described o-chloro benzonitrile solution, heated and stirred to 20 ℃-120 ℃;
Drip described sodium disulfide solution and react, the mol ratio of wherein said sodium disulfide and described o-chloro benzonitrile is 1:0.5-0.8;
The o-chloro benzonitrile mass percentage content stops less than 1.5% the time dripping in described reaction soln;
Standing demix, its oil-phase product are two sulfo-cyanophenyl solution,
Wherein said catalyzer is the organic amine salt compounds.
As of the present invention a kind of 1, a kind of preferred version of the preparation method of 2-BIT, wherein said 20 ℃-120 ℃ is 80 ℃-100 ℃.
As of the present invention a kind of 1, a kind of preferred version of the preparation method of 2-BIT, wherein saidly add catalyzer in described o-chloro benzonitrile solution, splash into subsequently described sodium disulfide solution and react and comprise: the o-chloro benzonitrile mass percentage content stops dripping less than 1.5% the time in described reaction soln.
as of the present invention a kind of 1, a kind of preferred version of the preparation method of 2-BIT, wherein said will add in described pair of sulfo-cyanophenyl solution water and cooling, passing into subsequently oxygenant reacts, the reaction later stage heats up, the final product 1 that generates, the 2-BIT comprises: be the solution of 1:1-5 with the mol ratio that adds water in described pair of sulfo-cyanophenyl solution and make two sulfo-cyanophenyls and water, and to be cooled to temperature be 0 ℃-80 ℃, pass into chlorine, SULPHURYL CHLORIDE, any one oxygenant in bromine and hydrogen peroxide reacts, it is 60 ℃-80 ℃ that the reaction later stage is warming up to temperature, described reaction is two sulfo-cyanophenyl mass percentage content stopped reaction less than 1.0% time in described reaction soln, the final product 1 that generates, the 2-BIT.
As of the present invention a kind of 1, a kind of preferred version of the preparation method of 2-BIT, wherein said 0 ℃-80 ℃ is 10 ℃-30 ℃.
This synthetic method with the sodium disulfide reaction, makes two sulfo-cyanophenyls take o-chloro benzonitrile as raw material, and two sulfo-cyanophenyls generate 1,2-BIT with the oxidant reaction cyclization again, and this method reduces the production cost of 1,2-BIT on the one hand; Improve on the other hand production environment, be beneficial to environmental protection.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the present invention is further detailed explanation below in conjunction with embodiment.
It is a kind of 1 that the present invention proposes, the preparation method of 2-BIT, and it comprises the steps or operates.
Step 1 is added to the water sodium sulphite and sulphur through reaction and makes sodium disulfide solution.
In one embodiment, this step can specific as followsly be carried out: sodium sulphite is added water be made into the aqueous solution that mass percent is 20%-50%; Add equimolar sulphur, heated and stirred is reacted under 70-100 ℃, until the whole solvent solns of sulphur are transparent, finally makes sodium disulfide solution.
Step 2 is dissolved in o-chloro benzonitrile and is made into o-chloro benzonitrile solution in organic solvent.
In one embodiment, this step can specific as followsly be carried out: o-chloro benzonitrile is dissolved in organic solvent, and being made into mass percent is the o-chloro benzonitrile solution of 20%-70%, and described organic solvent is any one in toluene, chlorobenzene and ethylene dichloride.
Step 3 adds catalyzer in described o-chloro benzonitrile solution, and splash into subsequently described sodium disulfide solution and react, standing demix after reaction, its oil-phase product is two sulfo-cyanophenyl solution.
In one embodiment, this step can specific as followsly be carried out: add catalyzer in described o-chloro benzonitrile solution, heated and stirred to 20 ℃-120 ℃; Drip described sodium disulfide solution and react, the mol ratio of wherein said sodium disulfide and described o-chloro benzonitrile is 1:0.5-0.8; The o-chloro benzonitrile mass percentage content stops less than 1.5% the time dripping in described reaction soln.Standing demix, its oil-phase product are two sulfo-cyanophenyl solution, and wherein said catalyzer is the organic amine salt compounds.
In another embodiment, this step can specific as followsly be carried out: add catalyzer in described o-chloro benzonitrile solution, heated and stirred to 80 ℃-100 ℃; Drip described sodium disulfide solution and react, the mol ratio of wherein said sodium disulfide and described o-chloro benzonitrile is 1:0.5-0.8; The o-chloro benzonitrile mass percentage content stops less than 1.5% the time dripping in described reaction soln.Standing demix, its oil-phase product are two sulfo-cyanophenyl solution, and wherein said catalyzer is the organic amine salt compounds.
Step 4 with adding water and cooling in described pair of sulfo-cyanophenyl solution, passes into subsequently oxygenant and reacts, and the reaction later stage heats up, and finally generates product 1, the 2-BIT.
In one embodiment, this step can specific as followsly be carried out: be the solution of 1:1-5 with the mol ratio that adds water in described pair of sulfo-cyanophenyl solution and make two sulfo-cyanophenyls and water, and to be cooled to temperature be 0 ℃-80 ℃, any one oxygenant that passes in chlorine, SULPHURYL CHLORIDE, bromine and hydrogen peroxide reacts, it is 60 ℃-80 ℃ that the reaction later stage is warming up to temperature, described reaction is two sulfo-cyanophenyl mass percentage content stopped reaction less than 1.0% time in described reaction soln, final product 1, the 2-BIT of generating.
In another embodiment, this step can specific as followsly be carried out: be the solution of 1:1-5 with the mol ratio that adds water in described pair of sulfo-cyanophenyl solution and make two sulfo-cyanophenyls and water, and to be cooled to temperature be 10 ℃-30 ℃, any one oxygenant that passes in chlorine, SULPHURYL CHLORIDE, bromine and hydrogen peroxide reacts, it is 60 ℃-80 ℃ that the reaction later stage is warming up to temperature, described reaction is two sulfo-cyanophenyl mass percentage content stopped reaction less than 1.0% time in described reaction soln, final product 1, the 2-BIT of generating.
It is elaborated to production method of the present invention below in conjunction with specific embodiment.
Embodiment one
0.55 mole of sodium sulphite solid is added in 100 ml waters, and being and being made into mass percent is 30% the aqueous solution, is heated with stirring to 80 ℃, add 18 gram sulfur reactions, hence one can see that, and sulphur equates with the amount of substance of sodium sulphite, continues to be heated to 90 ℃ of reactions 2 hours.The transparent clarification of gained solution.
1.0 moles of o-chloro benzonitriles are dissolved in 300 milliliters of toluene, being and being made into mass percent is 46.51% o-chloro benzonitrile solution, adds 6.0 gram catalyzer, stirs and is heated to 100 ℃, keep dripping above-mentioned preparation sodium disulfide solution at this temperature, approximately added in 2 hours.Dropwise rear continuation reaction 1 hour.Work as o-chloro benzonitrile content less than 1.5% the time by liquid chromatographic detection, reaction finishes.The system standing demix, lower aqueous layer is discharged, and the upper strata is two sulfo-cyanophenyl toluene solutions.With the two sulfo-cyanophenyl toluene solutions of 600 milliliters of moisture secondary washing, obtain pure pair of sulfo-cyanophenyl toluene solution.
The two sulfo-cyanophenyl solution of above-mentioned preparation are added 24 gram water, stir and be cooled to 15 ℃.Slowly pass into chlorine, and keep temperature of reaction at 15-30 ℃, logical chlorine was warming up to 70 ℃ of reactions 1 hour after 2 hours.Less than 1.0%, reaction finishes liquid chromatographic detection when two sulfo-cyanophenyl content.Filtration obtains 1, the thick product of 2-BIT and toluene solvant.Thick product is molten through alkali, decolouring, acid out, washing, drying obtain 123.8 grams 1, and 2-BIT finished product, content are 98.6%, and product yield is 80.9%.Solvent toluene is through the Distillation recovery reusable edible.
The present invention is not limited only to above embodiment.Those skilled in the art can use for reference this paper content, suitably improve or adjust content of the present invention and can realize.Special needs to be pointed out is, all are similarly replaced and change, and to those skilled in the art, are apparent, and they all are deemed to be included in the scope of the invention.
In sum, this synthetic method with the sodium disulfide reaction, makes two sulfo-cyanophenyls take o-chloro benzonitrile as raw material, and two sulfo-cyanophenyls generate 1,2-BIT with the oxidant reaction cyclization again.This method reduces the production cost of 1,2-BIT on the one hand; Improve on the other hand production environment, be beneficial to environmental protection.
It should be noted that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment, the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (7)
1. the preparation method of a 2-BIT, it comprises:
(1) sodium sulphite and sulphur are added to the water through reaction make sodium disulfide solution;
(2) o-chloro benzonitrile is dissolved in is made into o-chloro benzonitrile solution in organic solvent;
(3) add catalyzer in described o-chloro benzonitrile solution, splash into subsequently described sodium disulfide solution and react, standing demix after reaction, its oil-phase product is two sulfo-cyanophenyl solution;
(4) with adding water and cooling in described pair of sulfo-cyanophenyl solution, pass into subsequently oxygenant and react, the reaction later stage heats up, and finally generates product 1, the 2-BIT.
2. as claimed in claim 11, the preparation method of 2-BIT is characterized in that: make sodium disulfide solution through reaction comprise described sodium sulphite and sulphur be added to the water:
Sodium sulphite is added water be made into the aqueous solution that mass percent is 20%-50%;
Add equimolar sulphur, heated and stirred is reacted under 70-100 ℃, until the whole solvent solns of sulphur are transparent, finally makes sodium disulfide solution.
3. as claimed in claim 11, the preparation method of 2-BIT is characterized in that: described o-chloro benzonitrile is dissolved in is made into o-chloro benzonitrile solution and comprises in organic solvent:
O-chloro benzonitrile is dissolved in organic solvent, and being made into mass percent is the o-chloro benzonitrile solution of 20%-70%, and described organic solvent is any one in toluene, chlorobenzene and ethylene dichloride.
4. as claimed in claim 11, the preparation method of 2-BIT, it is characterized in that: describedly add catalyzer in described o-chloro benzonitrile solution, drip subsequently described sodium disulfide solution and react, standing demix after reaction, its oil-phase product comprises for two sulfo-cyanophenyl solution:
Add catalyzer in described o-chloro benzonitrile solution, heated and stirred to 20 ℃-120 ℃;
Drip described sodium disulfide solution and react, the mol ratio of wherein said sodium disulfide and described o-chloro benzonitrile is 1:0.5-0.8;
The o-chloro benzonitrile mass percentage content stops less than 1.5% the time dripping in described reaction soln;
Standing demix, its oil-phase product are two sulfo-cyanophenyl solution,
Wherein said catalyzer is the organic amine salt compounds.
5. as claimed in claim 41, the preparation method of 2-BIT is characterized in that: described 20 ℃-120 ℃ is 80 ℃-100 ℃.
6. as claimed in claim 11, the preparation method of 2-BIT, it is characterized in that: described will add in described pair of sulfo-cyanophenyl solution water and cooling, passing into subsequently oxygenant reacts, the reaction later stage heats up, the final product 1 that generates, the 2-BIT comprises: be the solution of 1:1-5 with the mol ratio that adds water in described pair of sulfo-cyanophenyl solution and make two sulfo-cyanophenyls and water, and to be cooled to temperature be 0 ℃-80 ℃, pass into chlorine, SULPHURYL CHLORIDE, any one oxygenant in bromine and hydrogen peroxide reacts, it is 60 ℃-80 ℃ that the reaction later stage is warming up to temperature, described reaction is two sulfo-cyanophenyl mass percentage content stopped reaction less than 1.0% time in described reaction soln, the final product 1 that generates, the 2-BIT.
7. as claimed in claim 61, the preparation method of 2-BIT is characterized in that: described 0 ℃-80 ℃ is 10 ℃-30 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817517A (en) * | 2015-04-24 | 2015-08-05 | 大丰跃龙化学有限公司 | Synthetic method of 1, 2-benzisothiazolin-3-one |
| CN104926751A (en) * | 2014-03-18 | 2015-09-23 | 胡俊 | Benzisothiazolone derivatives and synthetic method thereof |
| CN105801516A (en) * | 2016-04-28 | 2016-07-27 | 大丰跃龙化学有限公司 | Purification process of 1,2-benzisothiazolin-3-ketone |
| CN111072587A (en) * | 2019-12-18 | 2020-04-28 | 陕西中杰科仪化学科技有限公司 | Method for preparing benzo [ d ] isothiazoline-3 (2H) -ketone by catalyzing oxidation cyclization of molecular oxygen |
| CN115974809A (en) * | 2023-03-21 | 2023-04-18 | 北京探微精细化工科技有限公司 | Method for preparing benzo [ d ] isothiazoline-3 (2H) -ketone by oxygen transfer reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1081141A1 (en) * | 1994-07-05 | 2001-03-07 | Sumitomo Seika Chemicals Co., Ltd. | Method for producing 1,2-benzisothiazol-3-ones |
| CN102516133A (en) * | 2011-12-01 | 2012-06-27 | 浙江普洛医药科技有限公司 | Preparation method of methanesulfonic acid derivative |
| WO2012127969A1 (en) * | 2011-03-18 | 2012-09-27 | 住友精化株式会社 | 1,2-benzisothiazol-3-one compound production method |
-
2013
- 2013-03-22 CN CN2013100952306A patent/CN103172588A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1081141A1 (en) * | 1994-07-05 | 2001-03-07 | Sumitomo Seika Chemicals Co., Ltd. | Method for producing 1,2-benzisothiazol-3-ones |
| WO2012127969A1 (en) * | 2011-03-18 | 2012-09-27 | 住友精化株式会社 | 1,2-benzisothiazol-3-one compound production method |
| CN102516133A (en) * | 2011-12-01 | 2012-06-27 | 浙江普洛医药科技有限公司 | Preparation method of methanesulfonic acid derivative |
Non-Patent Citations (1)
| Title |
|---|
| 方永勤 等.: "N-甲基-1, 2-苯并异噻唑啉-3-酮的合成研究", 《化学世界》, no. 6, 25 June 2009 (2009-06-25), pages 361 - 363 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926751A (en) * | 2014-03-18 | 2015-09-23 | 胡俊 | Benzisothiazolone derivatives and synthetic method thereof |
| CN104817517A (en) * | 2015-04-24 | 2015-08-05 | 大丰跃龙化学有限公司 | Synthetic method of 1, 2-benzisothiazolin-3-one |
| CN105801516A (en) * | 2016-04-28 | 2016-07-27 | 大丰跃龙化学有限公司 | Purification process of 1,2-benzisothiazolin-3-ketone |
| CN105801516B (en) * | 2016-04-28 | 2018-05-04 | 大丰跃龙化学有限公司 | A kind of 1,2- benzisothiazole-3-ketones purifying technique |
| CN111072587A (en) * | 2019-12-18 | 2020-04-28 | 陕西中杰科仪化学科技有限公司 | Method for preparing benzo [ d ] isothiazoline-3 (2H) -ketone by catalyzing oxidation cyclization of molecular oxygen |
| CN115974809A (en) * | 2023-03-21 | 2023-04-18 | 北京探微精细化工科技有限公司 | Method for preparing benzo [ d ] isothiazoline-3 (2H) -ketone by oxygen transfer reaction |
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Application publication date: 20130626 |