CN104817517A - Synthetic method of 1, 2-benzisothiazolin-3-one - Google Patents
Synthetic method of 1, 2-benzisothiazolin-3-one Download PDFInfo
- Publication number
- CN104817517A CN104817517A CN201510203295.7A CN201510203295A CN104817517A CN 104817517 A CN104817517 A CN 104817517A CN 201510203295 A CN201510203295 A CN 201510203295A CN 104817517 A CN104817517 A CN 104817517A
- Authority
- CN
- China
- Prior art keywords
- synthetic method
- benzamide
- cyclodextrin
- reactor
- bit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a synthetic method of 1, 2-benzisothiazolin-3-one. According to the method, benzamide and sodium thiosulfate are allowed to react in the presence of carrier sodium thiosulfate and catalyst to generate the 1, 2-benzisothiazolin-3-one. The method has the advantages such that the cost is low, the steps are few, the yield is high and the environment friendliness is high.
Description
Technical field
The invention belongs to field of fine chemical, be specifically related to a kind of synthetic method of BIT.
Background technology
The synthesis technique of existing BIT mainly contains two kinds: one is raw material with anthranilic acid, makes two thiobenzoic acid, then through chloride, chlorination, obtained 1, the 2-BIT of ammonification; Another kind is with Gas chromatography or o-chlorobenzaldehyde for raw material, after thiol reactant, reoxidizes obtained 1, the 2-BIT of cyclization.
The first process choice chlorine uses as oxygenant, and chlorine is hypertoxic gas, and operational requirement is high, easily causes casualties after leakage, to level of management and the security measures proposition high request of enterprise.The second technique uses sodium methyl mercaptide as raw material, and this material has foul smell, transport and to use link to require high, and the thiomethyl alcohol toxicity discharged in residual thiomethyl alcohol and production process is very high, very big to human injury.
These two kinds of raw materials technology kinds are complicated, and market price of raw material is higher, is unfavorable for reducing costs, and improve enterprise profit.And all adopt multistep synthesis, aftertreatment technology is complicated, wastewater flow rate is comparatively large, easily causes environmental pollution.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of cost is low, synthesis step is few, the synthetic method of the simple BIT of aftertreatment technology..
For solving the problems of the technologies described above, the invention provides following technical scheme: a kind of synthetic method of BIT, it comprises:
(1) cyclodextrin, benzamide and water are added in reactor, stir after heating, continue in reactor, add catalyzer and Sulfothiorine;
(2) pass into air to react, adopt HPLC to detect, when conversion rate of products reaches more than 99%, stop passing into air and heating;
(3) reaction solution is imported in extraction kettle, with organic solvent, reaction solution is extracted, isolate organic phase and the aqueous solution;
(4) merge the organic phase that twice extraction obtains, remove organic solvent wherein under reduced pressure, obtain product BIT;
(5) aqueous solution is back in reactor, adds benzamide and Sulfothiorine in proportion;
(6) repeating step (2) is to step (6).
As a preferred embodiment of the synthetic method of BIT of the present invention, the wherein said aqueous solution needs to lower the temperature after often applying mechanically 2 times, and elimination inorganic salt sodium sulfate wherein, could continue to apply mechanically.
As a preferred embodiment of the synthetic method of BIT of the present invention, wherein said step (1) comprising:
Be that cyclodextrin and the benzamide of 0.01:1-0.05:1 adds in reactor by mol ratio, then be that the water of 4-10 times amount of benzamide amount adds reactor by massfraction;
Be heated to 40-100 DEG C, stir half an hour;
Add catalyzer and Sulfothiorine that massfraction is the 1%-10% of benzamide amount, wherein the mol ratio of Sulfothiorine and benzamide is 1.2:1.
As a preferred embodiment of the synthetic method of BIT of the present invention, wherein said cyclodextrin includes alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin and cyclodextrin derivative.
As a preferred embodiment of the synthetic method of BIT of the present invention, wherein said catalyzer comprises iron protochloride, ferrous sulfate, Iron diacetate, Iron nitrate, cuprous iodide, cuprous acetate, palladium chloride.
As of the present invention 1, a preferred embodiment of the synthetic method of 2-benzisothiazole-3-ketone, wherein said step (3) comprising: imported by reaction solution in extraction kettle, be heated to 40-80 DEG C, at twice reaction solution is extracted with the organic solvent of 3 times amount, isolate organic phase and the aqueous solution;
As a preferred embodiment of the synthetic method of BIT of the present invention, wherein said organic solvent comprises ethyl acetate, butylacetate, methylene dichloride, trichloromethane etc.
As of the present invention 1, a preferred embodiment of the synthetic method of 2-benzisothiazole-3-ketone, wherein said step (4) comprising: merge the organic phase that twice extraction obtains, after being heated to 50-90 DEG C, remove organic solvent wherein under reduced pressure, obtain product BIT.
Compared with prior art, the present invention is if any following beneficial effect:
One, cost is low, the low price of raw material, and cyclodextrin and catalyzer can recycleds, only consume reaction raw materials, can not additionally consume other material.
Two, step is few, and single step reaction replaces polystep reaction, reduces technology difficulty.
Three, the feature of environmental protection is high, using air as oxygenant, pollution-free, and the wastewater flow rate of aftertreatment reduces, and reduces environmental protection of enterprise pressure.
Four, yield is high, one-step reaction, decreases the invisible consumption of material.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Alleged herein " embodiment " or " embodiment " refers to special characteristic, structure or the characteristic that can be contained at least one implementation of the present invention.Different local in this manual " in one embodiment " occurred not all refers to same embodiment, neither be independent or optionally mutually exclusive with other embodiments embodiment.
The reaction formula of BIT of the present invention is
Embodiment one:
(1) alpha-cylodextrin of 11.35g and the benzamide of 105g add in the water of 420g to be warmed up in 40 DEG C and stir 30min.
Add catalyzer iron protochloride 6.3g and 189.6g Sulfothiorine.
(2) insulation passes into air, and HPLC detects, and conversion rate of products reaches more than 99%, stops blowing air.
(3) insulation is at 40 DEG C, extracts at twice, separate organic phase with the solvent ethyl acetate of triplication to reaction solution.
(4) merge the organic phase that twice extraction obtains, be incubated at 20 DEG C, solvent is fallen in underpressure distillation, obtains product 142.7g, and yield is 94.5%.
Embodiment two:
(1) beta-cyclodextrin of 56.75g and the benzamide of 105g add in the water of 1000g to be warmed up in 80 DEG C and stir 30min.
Add catalyzer cuprous iodide 9.5g and 189.6g Sulfothiorine.
(2) insulation passes into air, and HPLC detects, and conversion rate of products reaches more than 99%, stops blowing air.
(3) be cooled to 40 DEG C, at twice reaction solution extracted with the solvent ethyl acetate of triplication, separate organic phase.
(4) merge the organic phase that twice extraction obtains, be incubated at 20 DEG C, solvent is fallen in underpressure distillation, obtains product 142.7g, and yield is 94.5%.
Embodiment three:
(1) γ-cyclodextrin of 28.4g and the benzamide of 105g add in the water of 1500g to be warmed up in 60 DEG C and stir 30min.
Add catalyzer palladium chloride 8.8g and 189.6g Sulfothiorine.
(2) insulation passes into air, and HPLC detects, and conversion rate of products reaches more than 99%, stops blowing air.
(3) be cooled to 40 DEG C, at twice reaction solution extracted with the solvent ethyl acetate of triplication, separate organic phase.
(4) merge the organic phase that twice extraction obtains, be incubated at 20 DEG C, solvent is fallen in underpressure distillation, obtains product 142.7g, and yield is 94.5%.
Above-mentioned explanation fully discloses the specific embodiment of the present invention.It is pointed out that the scope be familiar with person skilled in art and any change that the specific embodiment of the present invention is done all do not departed to claims of the present invention.Correspondingly, the scope of claim of the present invention is also not limited only to previous embodiment.
Claims (8)
1. a synthetic method for 2-benzisothiazole-3-ketone, it comprises:
(1) cyclodextrin, benzamide and water are added in reactor, stir after heating, continue in reactor, add catalyzer and Sulfothiorine;
(2) pass into air to react, adopt HPLC to detect, when conversion rate of products reaches more than 99%, stop passing into air and heating;
(3) reaction solution is imported in extraction kettle, with organic solvent, reaction solution is extracted, isolate organic phase and the aqueous solution;
(4) merge the organic phase that twice extraction obtains, remove organic solvent wherein under reduced pressure, obtain product BIT;
(5) aqueous solution is back in reactor, adds benzamide and Sulfothiorine in proportion;
(6) repeating step (2) is to step (6).
2. the synthetic method of BIT according to claim 1, it is characterized in that: the described aqueous solution needs to lower the temperature after often applying mechanically 2 times, elimination inorganic salt sodium sulfate wherein, could continue to apply mechanically.
3. the synthetic method of BIT according to claim 1, is characterized in that: described step (1) comprising:
Be that cyclodextrin and the benzamide of 0.01:1-0.05:1 adds in reactor by mol ratio, then be that the water of 4-10 times amount of benzamide amount adds reactor by massfraction;
Be heated to 40-100 DEG C, stir half an hour;
Add catalyzer and Sulfothiorine that massfraction is the 1%-10% of benzamide amount, wherein the mol ratio of Sulfothiorine and benzamide is 1.2:1.
4. the synthetic method of BIT according to claim 3, is characterized in that: described cyclodextrin includes alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin and cyclodextrin derivative.
5. the synthetic method of BIT according to claim 3, is characterized in that: described catalyzer comprises iron protochloride, ferrous sulfate, Iron diacetate, Iron nitrate, cuprous iodide, cuprous acetate, palladium chloride.
6. the synthetic method of BIT according to claim 1, is characterized in that: described step (3) comprising:
Reaction solution is imported in extraction kettle, be heated to 40-80 DEG C, at twice reaction solution is extracted with the organic solvent of 3 times amount, isolate organic phase and the aqueous solution.
7. the synthetic method of BIT according to claim 6, is characterized in that: described organic solvent comprises ethyl acetate, butylacetate, methylene dichloride, trichloromethane etc.
8. according to claim 11, the synthetic method of 2-benzisothiazole-3-ketone, it is characterized in that: described step (4) comprising: merge the organic phase that twice extraction obtains, after being heated to 50-90 DEG C, remove organic solvent wherein under reduced pressure, obtain product BIT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510203295.7A CN104817517B (en) | 2015-04-24 | 2015-04-24 | The synthetic method of BIT |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510203295.7A CN104817517B (en) | 2015-04-24 | 2015-04-24 | The synthetic method of BIT |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104817517A true CN104817517A (en) | 2015-08-05 |
| CN104817517B CN104817517B (en) | 2016-08-31 |
Family
ID=53728018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510203295.7A Active CN104817517B (en) | 2015-04-24 | 2015-04-24 | The synthetic method of BIT |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104817517B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625001A (en) * | 2020-12-04 | 2021-04-09 | 大丰跃龙化学有限公司 | Synthesis method of 1, 2-benzisothiazolin-3-ketone |
| CN112898225A (en) * | 2020-12-09 | 2021-06-04 | 大丰跃龙化学有限公司 | Synthesis method of 1, 2-benzisothiazolin-3-ketone |
| CN115353496A (en) * | 2022-06-20 | 2022-11-18 | 连云港市三联化工有限公司 | Continuous production process of 1, 2-benzisothiazolin-3-one |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119645A (en) * | 1994-07-05 | 1996-04-03 | 住友精化株式会社 | Method for producing 1,2-benzisothiazol-3-ones 21678/01 |
| CN1246114A (en) * | 1996-12-20 | 2000-03-01 | 曾尼卡有限公司 | Process for making benzisothiazolin-3-ones |
| CN102491955A (en) * | 2011-12-08 | 2012-06-13 | 上海易摩生物科技有限公司 | Process method for synthesizing 1, 2-benzisothiazdin-3-ketone |
| CN103145638A (en) * | 2013-03-18 | 2013-06-12 | 上海添蓝生物科技有限公司 | New preparation method of 2-butyl-1,2-benzoisothiazolin-3-ketone (BBIT) |
| CN103172588A (en) * | 2013-03-22 | 2013-06-26 | 大丰跃龙化学有限公司 | Preparation method for 1,2-benzo isothiazolinone |
-
2015
- 2015-04-24 CN CN201510203295.7A patent/CN104817517B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119645A (en) * | 1994-07-05 | 1996-04-03 | 住友精化株式会社 | Method for producing 1,2-benzisothiazol-3-ones 21678/01 |
| CN1246114A (en) * | 1996-12-20 | 2000-03-01 | 曾尼卡有限公司 | Process for making benzisothiazolin-3-ones |
| CN102491955A (en) * | 2011-12-08 | 2012-06-13 | 上海易摩生物科技有限公司 | Process method for synthesizing 1, 2-benzisothiazdin-3-ketone |
| CN103145638A (en) * | 2013-03-18 | 2013-06-12 | 上海添蓝生物科技有限公司 | New preparation method of 2-butyl-1,2-benzoisothiazolin-3-ketone (BBIT) |
| CN103172588A (en) * | 2013-03-22 | 2013-06-26 | 大丰跃龙化学有限公司 | Preparation method for 1,2-benzo isothiazolinone |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625001A (en) * | 2020-12-04 | 2021-04-09 | 大丰跃龙化学有限公司 | Synthesis method of 1, 2-benzisothiazolin-3-ketone |
| CN112898225A (en) * | 2020-12-09 | 2021-06-04 | 大丰跃龙化学有限公司 | Synthesis method of 1, 2-benzisothiazolin-3-ketone |
| CN115353496A (en) * | 2022-06-20 | 2022-11-18 | 连云港市三联化工有限公司 | Continuous production process of 1, 2-benzisothiazolin-3-one |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104817517B (en) | 2016-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104817517A (en) | Synthetic method of 1, 2-benzisothiazolin-3-one | |
| NO20075770L (en) | Process and catalyst for the preparation of a crude oil product with a reduced content of MCR | |
| AU2018253450B2 (en) | Method for preparing azoxystrobin intermediates | |
| NO20075767L (en) | Process and catalyst for the preparation of a crude oil product with a reduced nitrogen content | |
| CN103193608B (en) | A kind of take veratrole as the method that veratraldehyde prepared by raw material | |
| CN104072565A (en) | High-yield simple preparation method of 17alpha-hydroxy progesterone | |
| CN104163802B (en) | The preparation method of thiazolamine-4-ethyl formate | |
| CN107162944A (en) | The preparation method of 2,3 dimethyl benzene methyl sulfides | |
| CN104961634A (en) | Method for preparing high yield pinacolone, and pesticide bactericide | |
| CN109053511A (en) | A kind of preparation method of the chloro- 6- (methylthiomethyl) of 2- | |
| CN104086488A (en) | Synthetic method of 2,4,6-tri-substituted pyrimidine compounds | |
| CN112898225A (en) | Synthesis method of 1, 2-benzisothiazolin-3-ketone | |
| CN105061137A (en) | Synthetic method for 4, 4'-bis(chloromethyl) biphenyl | |
| Qu et al. | Chelation controlled reductive amination of cyclic ketones to trans-4-methoxycyclohexylamines: 9-BBN reduction mediated with FeCl3 | |
| CN103539631B (en) | Photochemical synthesis method for preparing chloroaromatics compound through halogen conversion reaction | |
| CN105152829B (en) | Method for synthesizing ketones from methyl tertiary alcohol | |
| CN103333072B (en) | Preparation method of 2-ethylaniline | |
| CN104557825B (en) | A kind of method reclaiming 3-(α-methoxyl group)-methylenebenzofuran-2 (3 hydrogen)-one | |
| CN104098527B (en) | A kind of preparation method of 5-methoxyl group-2-mercaptobenzothiazole | |
| CN103848794B (en) | The synthetic method of isatoic anhydride and derivative thereof | |
| CN107098817A (en) | 2,6- of one kind dichlor-4-trifluoromethyl anilines lead to chlorine production technology | |
| CN102653519A (en) | Method for preparing 2-aryl-thioacetamide | |
| CN104072910B (en) | The preparation method of PVC composition and PVC | |
| Pocklington | The Gulf of St. Lawrence and the Baltic Sea: a comparison of two organic systems | |
| CN101412682B (en) | Process for synthesizing aryl anthranilic acid and derivatives thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |