CN104817517B - The synthetic method of BIT - Google Patents
The synthetic method of BIT Download PDFInfo
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- CN104817517B CN104817517B CN201510203295.7A CN201510203295A CN104817517B CN 104817517 B CN104817517 B CN 104817517B CN 201510203295 A CN201510203295 A CN 201510203295A CN 104817517 B CN104817517 B CN 104817517B
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- Prior art keywords
- bit
- synthetic method
- benzamide
- cyclodextrin
- ferrous
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The synthetic method of 1,2 benzisothiazole 3 ketone of the present invention, its be use benzamide and sodium thiosulfate in the case of having carrier rings dextrin and catalyst, the method for reaction generation 1,2 benzisothiazole 3 ketone.The synthetic method of 1,2 benzisothiazole 3 ketone of the present invention has low cost, step is few, yield is high, feature of environmental protection advantages of higher.
Description
Technical field
The invention belongs to field of fine chemical, be specifically related to the synthesis side of a kind of BIT
Method.
Background technology
The synthesis technique of existing BIT mainly has two kinds: one is with adjacent aminobenzene
Formic acid is raw material, makes double thiobenzoate, then prepares 1 through chloride, chlorination, ammonification, 2-benzisothia
Oxazoline ketone；Another kind is with Gas chromatography or o-chlorobenzaldehyde as raw material, after thiol reactant, reoxidizes
Cyclization prepares 1,2-BIT.
The first process choice chlorine uses as oxidant, and chlorine is severe toxicity gas, and operation requires height,
Easily causing casualties after leakage, management level and safety measure to enterprise propose high request.The second
Technique uses sodium methyl mercaptide as raw material, and this material has foul smell, transports and uses link requirement high,
And the methanthiol toxicity of release is the highest in the methanthiol remained and production process, very big to human injury.
Both raw materials technology kinds are complicated, and market price of raw material is higher, are unfavorable for reducing cost, carry
High enterprise profit.And all using multistep synthesis, aftertreatment technology is complicated, and wastewater flow rate is relatively big, easily causes ring
Environment pollution.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of low cost, synthesis step is few, aftertreatment technology is simple
The synthetic method of single BIT..
For solving above-mentioned technical problem, the present invention provides following technical scheme: a kind of 1,2-benzisothiazole
The synthetic method of-3-ketone, comprising:
(1) cyclodextrin, benzamide and water are added in reactor, stir after heating, continue to reaction
Still adds catalyst and sodium thiosulfate；
(2) it is passed through air to react, uses HPLC detection, when conversion rate of products reaches more than 99%,
Stop being passed through air and heating；
(3) reactant liquor is imported in extraction kettle, with organic solvent, reactant liquor is extracted, isolate organic
Phase and aqueous solution；
(4) merge the organic facies being obtained by extraction for twice, remove organic solvent therein under reduced pressure, obtain product 1,
2-benzisothiazole-3-ketone；
(5) aqueous solution is back in reactor, adds benzamide and sodium thiosulfate in proportion；
(6) step (2) to step (6) is repeated.
As a preferred embodiment of the synthetic method of BIT of the present invention, its
Described in aqueous solution need to lower the temperature after often applying mechanically 2 times, filter off inorganic salt sodium sulfate therein,
Can continue to apply mechanically.
As a preferred embodiment of the synthetic method of BIT of the present invention, its
Described in step (1) including:
Cyclodextrin and benzamide that mol ratio is 0.01:1-0.05:1 are added in reactor, then by mass fraction is
The water of the 4-10 times amount of benzamide amount adds reactor；
It is heated to 40-100 DEG C, stirs half an hour；
Add catalyst and sodium thiosulfate, the wherein thiosulfuric acid of the 1%-10% that mass fraction is benzamide amount
Sodium is 1.2:1 with the mol ratio of benzamide.
As a preferred embodiment of the synthetic method of BIT of the present invention, its
Described in cyclodextrin include alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin and cyclodextrin derivative.
As a preferred embodiment of the synthetic method of BIT of the present invention, its
Described in catalyst include ferrous chloride, ferrous sulfate, Ferrous acetate, ferrous nitrate, Hydro-Giene (Water Science)., vinegar
Cuprous, the palladium chloride of acid.
As a preferred embodiment of the synthetic method of BIT of the present invention, its
Described in step (3) including: reactant liquor is imported in extraction kettle, is heated to 40-80 DEG C, with having of 3 times amount
Reactant liquor is extracted by machine solvent at twice, isolates organic facies and aqueous solution；
As a preferred embodiment of the synthetic method of BIT of the present invention, its
Described in organic solvent include ethyl acetate, butyl acetate, dichloromethane, chloroform etc..
As a preferred embodiment of the synthetic method of BIT of the present invention, its
Described in step (4) including: merge the organic facies being obtained by extraction for twice, after being heated to 50-90 DEG C, decompression steam
Except organic solvent therein, obtain product BIT.
Compared with prior art, the present invention such as has the advantages that:
One, low cost, the low price of raw material, and cyclodextrin and catalyst can only need with recycled
Consumption reaction raw materials, will not additionally consume other material.
Two, step is few, and single step reaction replaces multistep reaction, reduces technology difficulty.
Three, the feature of environmental protection is high, using air as oxidant, pollution-free, and the wastewater flow rate of post processing reduces, and reduces
Environmental protection of enterprise pressure.
Four, yield is high, and one-step reaction decreases the invisible consumption of material.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
" embodiment " or " embodiment " referred to herein refers to may be included in the present invention, and at least one is real
Special characteristic, structure or characteristic in existing mode.Different local in this manual occur " a reality
Execute in example " not refer both to same embodiment, it is not single or the most mutual with other embodiments
The embodiment repelled.
The reaction formula of BIT of the present invention is
Embodiment one:
(1) benzamide of the alpha-cyclodextrin of 11.35g and 105g is warmed up in 40 DEG C stir in adding the water of 420g
Mix 30min.
Add catalyst ferrous chloride 6.3g and 189.6g sodium thiosulfate.
(2) insulation is passed through air, and HPLC detects, and conversion rate of products reaches more than 99%, stops blowing air.
(3) insulation is at 40 DEG C, extracts reactant liquor at twice with the solvent ethyl acetate of triplication, point
Go out organic facies.
(4) merging the organic facies being obtained by extraction for twice, insulation is at 20 DEG C, and decompression distills solvent, is produced
Product 142.7g, yield is 94.5%.
Embodiment two:
(1) benzamide of the beta-schardinger dextrin-of 56.75g and 105g is warmed up in 80 DEG C stir in adding the water of 1000g
Mix 30min.
Add catalyst Hydro-Giene (Water Science). 9.5g and 189.6g sodium thiosulfate.
(2) insulation is passed through air, and HPLC detects, and conversion rate of products reaches more than 99%, stops blowing air.
(3) it is cooled to 40 DEG C, at twice reactant liquor is extracted with the solvent ethyl acetate of triplication, point
Go out organic facies.
(4) merging the organic facies being obtained by extraction for twice, insulation is at 20 DEG C, and decompression distills solvent, is produced
Product 142.7g, yield is 94.5%.
Embodiment three:
(1) benzamide of the gamma-cyclodextrin of 28.4g and 105g is warmed up in 60 DEG C stirring in adding the water of 1500g
30min。
Add catalyst palladium chloride 8.8g and 189.6g sodium thiosulfate.
(2) insulation is passed through air, and HPLC detects, and conversion rate of products reaches more than 99%, stops blowing air.
(3) it is cooled to 40 DEG C, at twice reactant liquor is extracted with the solvent ethyl acetate of triplication, point
Go out organic facies.
(4) merging the organic facies being obtained by extraction for twice, insulation is at 20 DEG C, and decompression distills solvent, is produced
Product 142.7g, yield is 94.5%.
Described above the most fully discloses the detailed description of the invention of the present invention.It is pointed out that and be familiar with being somebody's turn to do
Any change that the detailed description of the invention of the present invention is done by the technical staff in field is all without departing from the power of the present invention
The scope of profit claim.Correspondingly, the scope of the claim of the present invention is also not limited only to aforementioned tool
Body embodiment.
Claims (7)
1. a synthetic method for BIT, comprising:
(1) cyclodextrin, benzamide and water are added in reactor, stir after heating, continue to add the one in catalyst ferrous chloride, ferrous sulfate, Ferrous acetate, ferrous nitrate, Hydro-Giene (Water Science)., cuprous acetate, palladium chloride and sodium thiosulfate in reactor；
(2) it is passed through air to react, uses HPLC detection, when conversion rate of products reaches more than 99%, stop being passed through air and heating；
(3) reactant liquor is imported in extraction kettle, with organic solvent, reactant liquor is extracted, isolate organic facies and aqueous solution；
(4) merge the organic facies being obtained by extraction for twice, remove organic solvent therein under reduced pressure, obtain product BIT；
(5) aqueous solution is back in reactor, adds benzamide and sodium thiosulfate in proportion；
(6) step (2) to step (6) is repeated.
The synthetic method of BIT the most according to claim 1, it is characterised in that: described aqueous solution needs to lower the temperature after often applying mechanically 2 times, filters off inorganic salt sodium sulfate therein, could continue to apply mechanically.
The synthetic method of BIT the most according to claim 1, it is characterised in that: described step (1) including:
Cyclodextrin and benzamide that mol ratio is 0.01:1-0.05:1 are added in reactor, then the water of the 4-10 times amount that mass fraction is benzamide amount is added reactor；
It is heated to 40-100 DEG C, stirs half an hour；
Adding mass fraction is the one in the catalyst ferrous chloride of 1%-10% of benzamide amount, ferrous sulfate, Ferrous acetate, ferrous nitrate, Hydro-Giene (Water Science)., cuprous acetate, palladium chloride and sodium thiosulfate, and wherein sodium thiosulfate is 1.2:1 with the mol ratio of benzamide.
The synthetic method of BIT the most according to claim 3, it is characterised in that: described cyclodextrin includes alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin and cyclodextrin derivative.
The synthetic method of BIT the most according to claim 1, it is characterised in that: described step (3) including:
Reactant liquor is imported in extraction kettle, be heated to 40-80 DEG C, at twice reactant liquor is extracted with the organic solvent of 3 times amount, isolate organic facies and aqueous solution.
The synthetic method of BIT the most according to claim 5, it is characterised in that: described organic solvent includes ethyl acetate, butyl acetate, dichloromethane, chloroform.
The most according to claim 11, the synthetic method of 2-benzisothiazole-3-ketone, it is characterized in that: described step (4) including: merge the organic facies being obtained by extraction for twice, after being heated to 50-90 DEG C, remove organic solvent therein under reduced pressure, obtain product BIT.
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| CN201510203295.7A CN104817517B (en) | 2015-04-24 | 2015-04-24 | The synthetic method of BIT |
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| CN201510203295.7A CN104817517B (en) | 2015-04-24 | 2015-04-24 | The synthetic method of BIT |
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| CN104817517B true CN104817517B (en) | 2016-08-31 |
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| 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 |
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| US5633384A (en) * | 1994-07-05 | 1997-05-27 | Sumitomo Seika Chemicals Co., Ltd. | Method for producing 1,2-benzisothiazol-3-ones |
| GB9626570D0 (en) * | 1996-12-20 | 1997-02-05 | Zeneca Ltd | 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 |
| CN103145638B (en) * | 2013-03-18 | 2015-05-27 | 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 |
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