CN104529932A - Synthesis method of 2-butyl-1,2-benzisothiazolin-3-one - Google Patents
Synthesis method of 2-butyl-1,2-benzisothiazolin-3-one Download PDFInfo
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- CN104529932A CN104529932A CN201410811309.9A CN201410811309A CN104529932A CN 104529932 A CN104529932 A CN 104529932A CN 201410811309 A CN201410811309 A CN 201410811309A CN 104529932 A CN104529932 A CN 104529932A
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- 0 *=CN1Sc2ccccc2C1=O Chemical compound *=CN1Sc2ccccc2C1=O 0.000 description 1
- VOABTHMZKCEUIU-UHFFFAOYSA-N CCCCNC(c(cccc1)c1SSc1cc(CCC)ccc1C(NC)=O)=O Chemical compound CCCCNC(c(cccc1)c1SSc1cc(CCC)ccc1C(NC)=O)=O VOABTHMZKCEUIU-UHFFFAOYSA-N 0.000 description 1
- NECMWXVJIUGCSW-UHFFFAOYSA-N COC(c1ccccc1SSc1ccccc1C(OC)=O)=O Chemical compound COC(c1ccccc1SSc1ccccc1C(OC)=O)=O NECMWXVJIUGCSW-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
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Abstract
The invention discloses a synthesis method of 2-butyl-1,2-benzisothiazolin-3-one. The synthesis method comprises the following steps: by taking bis-sulpho-cyanophenyl and alcohol as raw materials, carrying out a Pinner reaction to generate a Pinner salt under acid catalysis, hydrolyzing the Pinner salt to generate bis-sulpho-benzoate, recovering the catalyst and the alcohol, adding alcohol solvents, adding n-butylamine in the reaction solution and carrying out an amidation reaction, and recovering the solvent under a reduced pressure to obtain 2,2'-dithio-dibenzamide; dissolving 2,2'-dithio-dibenzamide in an organic solvent, adding a chlorination agent and cyclizing to generate 2-butyl-1,2-benzisothiazolin-3-one. According to the synthesis method disclosed by the invention, environment-friendly raw materials are used, thus reducing environment pollution; meanwhile, the whole synthesis process of the synthesis method disclosed by the invention is a one-pot method, a middle separation process is not needed, the operation is convenient, the whole reaction process is high in yield, the purity of the obtained target product is also relatively high; the synthesis method is low in pollution, high in yield and high in purity.
Description
Technical field
The present invention relates to the synthetic method of a kind of 2-butyl-BIT, belong to field of fine chemical.
Background technology
2-butyl-1; 2-benzisothiazole-3-ketone is as a kind of wide spectrum, efficiently sterilant; in widespread use industrial or agricultural; it is mainly used in the erosion of the polymers such as protection PCV, urethane, silica column, polyolefine, polyester from bacterium, mould, algae etc., and can give surfactivity to improve plastics and coating dry film antibacterial surface effect.The synthetic method of current report has several as follows: method 1. is with 2,2 '-dithiodibenzoic acid is starting raw material, through chloride, ammonia solution preocess synthesis N, N '-dibutyl-2,2 '-dithio dibenzamide, then react with Sodium Pyrosulfite and generate bunte salts (Bunte salt), last alkaline cyclization obtains 2-butyl-1,2-benzisothiazole-3-ketone, the reaction formula of whole process is:
Aforesaid method in acyl chloride reaction one step, be no matter with thionyl chloride or phosphorus trichloride, phosgene etc. as chlorizating agent, all can bring serious problem of environmental pollution.Simultaneously in ammonia solution one step, when acyl chlorides and n-Butyl Amine 99 react, be the hydrogen chloride gas that neutralization generates, need the organic bases of twice equivalent, cause raw materials cost greatly to improve.
Method 2. is reacted with halo normal butane by the metal-salt of BIT, synthesizes 2-butyl-BIT.
While synthesis primary product 2-butyl-BIT, also there is O-alkylation side reaction, cause the poor selectivity of whole reaction, purify more difficult in aforesaid method.
Method 3. take o-chloro benzonitrile as raw material, reacts generate methylmercapto cyanophenyl with sodium methyl mercaptide, then synthesizes N-normal-butyl methylmercapto benzamide, obtains 2-butyl-BIT through cyclisation.
Aforesaid method sulfuration one step adopts sodium methyl mercaptide to be raw material, and this unstripped gas smells foul, and produces a large amount of difficult waste water in operating process, very large to environmental influence.
Above-mentioned said all methods are all periodical operation, whole treating processes all very loaded down with trivial details.
Summary of the invention
The present invention is directed to the shortcoming of aforesaid method, a kind of high reaction preference, high yield, low stain, synthesis 2-butyl-BIT method easy and simple to handle are provided.Concrete technical scheme of the present invention is as follows.
The application provides a kind of with the method for two sulfo-cyanophenyl for main raw material synthesis 2-butyl-BIT, specifically comprises the steps:
(1) with two sulfo-cyanophenyl and alcohol for raw material, under acid catalysis, there is Pinner reaction and generate Pinner salt;
(2) in the reaction solution of step (1), drip water, continue reaction, Pinner salt hydrolysis generates two Thiobenzoate, reclaims catalyzer and alcohol;
(3) alcohol and n-Butyl Amine 99 are added in the reaction solution of above-mentioned steps (2) and carry out amidate action, decompression and solvent recovery obtains 2,2 '-dithio dibenzamide;
(4) 2,2 '-dithio dibenzamide is dissolved in organic solvent, adds chlorination reagent cyclization and generate 2-butyl-BIT.
Preferably, the acid described in above-mentioned steps (1) is hydrogenchloride.
Preferably, above-mentioned, the Pinner temperature of reaction described in step (1) is 45-80
0c, the reaction times is 4-12 hour.
Preferably, above-mentioned steps (1) and the alcohol described in (2) are the one in methyl alcohol, ethanol, propyl alcohol or other lower alkyl alcohols.
More preferably, described alcohol is methyl alcohol.
Preferably, the organic solvent described in above-mentioned steps (4) is any one in toluene, dimethylbenzene, chlorobenzene, zellon.
Preferably, the chlorination reagent described in above-mentioned steps (4) be in SULPHURYL CHLORIDE, chlorine, bromine any one.
Further, described in the application, the mol ratio of two sulfo-cyanophenyl and n-Butyl Amine 99 is 1:2.0-2.1.
Further, described in the application, the mol ratio of two sulfo-cyanophenyl and chlorination reagent is 1:1.0-1.5.
Further, in the application, the condition of step (4) described ring-closure reaction is: temperature 60-70
0c, pH value is 3-4, and the reaction times is 30 minutes.
In simple terms, the Reactive Synthesis route that provides of the application is as follows:
Namely, with two sulfo-cyanophenyl and alcohol for raw material, under acid catalysis, Pinner reaction occurs and generates Pinner salt, Pinner salt hydrolysis generates two Thiobenzoate, reclaims catalyzer and alcohol (can recycle), add alcoholic solvent, added in above-mentioned reaction solution by n-Butyl Amine 99 and carry out amidate action, decompression and solvent recovery obtains 2,2 '-dithio dibenzamide; 2,2 '-dithio dibenzamide is dissolved in organic solvent, adds chlorination reagent cyclization and generate 2-butyl-BIT.
Beneficial effect: the method relatively reported, the present invention uses environment amenable raw material, reduce environmental pollution, the whole building-up process of the present invention is simultaneously one kettle way, do not need middle sepn process, handled easily, not only yield target product purity that is high, that obtain is also relatively high for whole reaction process.The present invention is a kind of low stain, high yield, highly purified synthetic method.
Embodiment
Below by embodiment, the present invention is described in further details.
Embodiment 1
By two sulfo-cyanophenyl (268g, 1mol) add in reaction flask, add saturated hydrogen chloride methanol solution 1340g, be heated to backflow, stirring reaction is after 6 hours, drip water (27g, 1.5mol), continue reaction after 0.5 hour, Distillation recovery hydrogen chloride methanol solution, stopped reaction is down to room temperature, add methyl alcohol 1074g and n-Butyl Amine 99 (148g, 2.02mol) be warming up to backflow, continue reaction 5 hours, decompression and solvent recovery, add chlorobenzene 1200g, obtain 2, 2 '-dithio dibenzamide chlorobenzene solution, under stirring at room temperature, to above-mentioned 2, 2 '-dithio dibenzamide chlorobenzene solution passes into chlorine 78g(1.1mol), be warming up to 60
0c discharges acid gas, be down to room temperature, the 400g that adds water washes organic layer, be 3 by saturated aqueous sodium carbonate adjust ph subsequently, and stir 30 minutes, washing organic layer, decompression and solvent recovery, obtain faint yellow oily 2-butyl-BIT 377g (HPLC > 98 %), yield is 91%.
Embodiment 2
By two sulfo-cyanophenyl (268g, 1mol) add in reaction flask, add saturated ethanol solution of hydrogen chloride 1200g, be heated to backflow, stirring reaction is after 8 hours, drip water (21.6g, 1.2mol), continue reaction after 0.5 hour, stopped reaction is down to room temperature, Distillation recovery ethanol solution of hydrogen chloride, add ethanol 1206g and n-Butyl Amine 99 (148g, 2.02mol) be warming up to backflow, continue reaction 10 hours, decompression and solvent recovery, add zellon 1206g, obtain 2, 2 '-dithio dibenzamide zellon solution, under stirring at room temperature, to above-mentioned 2, 2 '-dithio dibenzamide zellon solution drips bromine (208g, 1.3mol), be warming up to 70
0c discharges acid gas, be down to room temperature, the 400g that adds water washes organic layer, be 4 by saturated aqueous sodium carbonate adjust ph subsequently, and stir 30 minutes, washing organic layer, decompression and solvent recovery, obtain faint yellow oily 2-butyl-BIT 382g (HPLC > 98 %), yield is 92 %.
Embodiment 3
By two sulfo-cyanophenyl (268g, 1mol) add in reaction flask, add saturated hydrogenchloride propanol solution 1000g, be heated to backflow, stirring reaction is after 12 hours, drip water (27g, 1.5mol), continue reaction after 0.5 hour, Distillation recovery hydrogenchloride propanol solution, stopped reaction is down to room temperature, add propyl alcohol 1000g and n-Butyl Amine 99 (153g, 2.1mol) be warming up to backflow, continue reaction 7 hours, decompression and solvent recovery, add chlorobenzene 1200g, obtain 2, 2 '-dithio dibenzamide chlorobenzene solution, under stirring at room temperature, to above-mentioned 2, 2 '-dithio dibenzamide chlorobenzene solution passes into chlorine (106g, 1.5mol), be warming up to 65
0c discharges acid gas, be down to room temperature, the 400g that adds water washes organic layer, be 3 by saturated aqueous sodium carbonate adjust ph subsequently, and stir 30 minutes, washing organic layer, decompression and solvent recovery, obtain faint yellow oily 2-butyl-BIT 386g (HPLC > 98 %), yield is 93%.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (10)
1. a synthetic method for 2-butyl-BIT, is characterized in that, described method comprises the steps:
(1) with two sulfo-cyanophenyl and alcohol for raw material, under acid catalysis, there is Pinner reaction and generate Pinner salt;
(2) in the reaction solution of step (1), drip water, continue reaction, Pinner salt hydrolysis generates two Thiobenzoate, reclaims catalyzer and alcohol;
(3) alcohol and n-Butyl Amine 99 are added in the reaction solution of above-mentioned steps (2) and carry out amidate action, decompression and solvent recovery obtains 2,2 '-dithio dibenzamide;
(4) 2,2 '-dithio dibenzamide is dissolved in organic solvent, adds chlorination reagent cyclization and generate 2-butyl-BIT.
2. the synthetic method of a kind of 2-butyl-BIT according to claim 1, it is characterized in that, the acid described in step (1) is hydrogenchloride.
3. the synthetic method of a kind of 2-butyl-BIT according to claim 1, it is characterized in that, the Pinner temperature of reaction described in step (1) is 45-80
0c, the reaction times is 4-12 hour.
4. the synthetic method of a kind of 2-butyl-BIT according to claim 1, is characterized in that, described alcohol is the one in methyl alcohol, ethanol, propyl alcohol or other lower alkyl alcohols.
5. the synthetic method of a kind of 2-butyl-BIT according to claim 4, it is characterized in that, described alcohol is methyl alcohol.
6. the synthetic method of a kind of 2-butyl-BIT according to claim 1, is characterized in that, the organic solvent described in step (4) is any one in toluene, dimethylbenzene, chlorobenzene, zellon.
7. the synthetic method of a kind of 2-butyl-BIT according to claim 1, is characterized in that, the chlorination reagent described in step (4) be in SULPHURYL CHLORIDE, chlorine, bromine any one.
8. the synthetic method of a kind of 2-butyl-BIT according to claim 1, is characterized in that, the mol ratio of described pair of sulfo-cyanophenyl and n-Butyl Amine 99 is 1:2.0-2.1.
9. the synthetic method of a kind of 2-butyl-BIT according to claim 1, the mol ratio of described pair of sulfo-cyanophenyl and chlorination reagent is 1:1.0-1.5.
10. the synthetic method of a kind of 2-butyl-BIT according to claim 1, the condition of step (4) described ring-closure reaction is: temperature 60-70
0c, pH value is 3-4, and the reaction times is 30 minutes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483438A (en) * | 2019-09-09 | 2019-11-22 | 大连百傲化学股份有限公司 | A kind of duct type continuous production method of 3- iso thiazoline ketone compound |
| 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 |
| CN111253335A (en) * | 2020-03-12 | 2020-06-09 | 浙江扬帆新材料股份有限公司 | Novel synthesis method of N-substituted benzisothiazolin-3-one derivative |
| CN114181124A (en) * | 2021-12-13 | 2022-03-15 | 大连百傲化学股份有限公司 | Recycling treatment method of 1, 2-benzisothiazolin-3-one chlorination process wastewater |
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| US4736040A (en) * | 1985-01-10 | 1988-04-05 | Basf Aktiengesellschaft | Preparation of 1,2-benzisothiazolones |
| US20060128984A1 (en) * | 2002-07-25 | 2006-06-15 | Alain Chenede | Method of preparing an ester of an aromatic carboxylic acid bearing at least one perfluoroalkyl group |
| JP2007223957A (en) * | 2006-02-24 | 2007-09-06 | Fujifilm Corp | Method for producing benzoic acid ester |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483438A (en) * | 2019-09-09 | 2019-11-22 | 大连百傲化学股份有限公司 | A kind of duct type continuous production method of 3- iso thiazoline ketone compound |
| CN110483438B (en) * | 2019-09-09 | 2023-10-10 | 大连百傲化学股份有限公司 | Pipeline type continuous production method of 3-isothiazolinone compound |
| 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 |
| CN111253335A (en) * | 2020-03-12 | 2020-06-09 | 浙江扬帆新材料股份有限公司 | Novel synthesis method of N-substituted benzisothiazolin-3-one derivative |
| CN111253335B (en) * | 2020-03-12 | 2023-06-06 | 浙江扬帆新材料股份有限公司 | New synthetic method of N-substituted benzisothiazolin-3-one derivative |
| CN114181124A (en) * | 2021-12-13 | 2022-03-15 | 大连百傲化学股份有限公司 | Recycling treatment method of 1, 2-benzisothiazolin-3-one chlorination process wastewater |
| CN114181124B (en) * | 2021-12-13 | 2024-01-26 | 大连百傲化学股份有限公司 | Recycling treatment method of 1, 2-benzisothiazolin-3-one chlorination process wastewater |
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Application publication date: 20150422 |