CN109456282A - A kind of synthetic method of 2- chloro benzothiazole - Google Patents
A kind of synthetic method of 2- chloro benzothiazole Download PDFInfo
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- CN109456282A CN109456282A CN201910024834.9A CN201910024834A CN109456282A CN 109456282 A CN109456282 A CN 109456282A CN 201910024834 A CN201910024834 A CN 201910024834A CN 109456282 A CN109456282 A CN 109456282A
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- benzothiazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
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- Thiazole And Isothizaole Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of synthetic methods of 2- chloro benzothiazole, synthesize 2- chloro benzothiazole through chlorine direct chlorination by benzothiazole；Specifically includes the following steps: being added the atent solvent of metering and benzothiazole, catalyst in cooler and device for absorbing tail gas, the reactor that can be stirred and have chlorine ingress pipe, heating starts the chlorine reaction for being continually fed into metering；After reaction, it then is post-processed and obtains 2- chloro benzothiazole.The features such as there is the present invention raw material to be easy to get, simple process, easy to operate, reaction condition is mild, solvent recoverable, and yield is higher, high-quality, be suitble to industrialized production；Production cost is reduced, the pollution to environment is reduced.
Description
Technical field
The present invention relates to a kind of synthetic methods of 2- chloro benzothiazole.
Background technique
It is Material synthesis that the synthetic method of document report 2- chloro benzothiazole, which is by 2-mercaptobenzothiazole, at present.Mainly have
Following several method;
(1) phosgenation: 2-mercaptobenzothiazole is added in toluene, and 60 DEG C or so whens are passed through phosgene, and reaction generates 2- chlorobenzene
And thiazole.It is washed, is layered, obtain high-content 2- chloro benzothiazole after carrying out precipitation treatment.This is also the master of current industrialized production
Want method.But in this method, cause risk in technical process bigger due to using raw material phosgene, production cost compares
Height, and the carbonyl sulfide gas generated brings difficulty to post-processing.
(2) thionyl chloride chloridising: 2-mercaptobenzothiazole is added in dichloroethanes, and chlorine is added dropwise in when (40~60) DEG C
Change sulfoxide, reaction generates 2- chloro benzothiazole.A large amount of sulfur dioxide can be generated in the reaction process of this method and hydrogen chloride is useless
Gas, environmental pollution is serious.Industrially it is rarely employed.
(3) chlorinated with chlorine method: 2-mercaptobenzothiazole is added in dichloroethanes, and when (40~60) DEG C is passed through chlorine,
Reaction generates 2- chloro benzothiazole.The product quality and yield of this method synthesis be not high, and can generate in reaction process a large amount of
Hydrogen sulfide and hydrogen chloride emission, environmental pollution is serious, it is difficult to realize industrialized production.Industrially it is rarely employed.
(4) Chinese patent CN201710415427 discloses a kind of synthetic method of 2- chloro benzothiazole: by 2- sulfydryl benzene
And thiazole is dispersed in water to form paste 2-mercaptobenzothiazole, then with 30% mixed in hydrochloric acid it is uniform mixture；In (35~
45) hydrogen peroxide DEG C, is added dropwise and carries out oxi-chlorination, insulation reaction to the 2-mercaptobenzothiazole content detected in system is lower than
Stop that hydrogen peroxide is added dropwise when 0.2%；It is 2- chloro benzothiazole crude product that upper layer oily liquids is taken after stratification.The reality of the invention
Matter is hydrochloric acid to be oxidized to hypochlorous acid, then carry out oxi-chlorination.The process can generate a large amount of sulfur-containing waste water；If oxychlorination
Misoperation, can also generate the hydrogen sulfide gas of severe toxicity, and post-processing is more difficult.Have no industrialization report.
(5) it there are no using benzothiazole as raw material, synthesize the method document report of 2- chloro benzothiazole.
Summary of the invention
The purpose of the present invention is to provide a kind of reduction production costs, reduce the 2- chloro benzothiazole of the pollution to environment
Synthetic method.
The technical solution of the invention is as follows:
A kind of synthetic method of 2- chloro benzothiazole, it is characterised in that: synthesize 2- chlorobenzene through chlorine direct chlorination by benzothiazole
And thiazole；Specifically includes the following steps: the atent solvent of metering and benzothiazole, catalyst to be added and have cooler and tail gas
It in absorption plant, the reactor that can be stirred and have chlorine ingress pipe, heats up, the chlorine for starting to be continually fed into metering is anti-
It answers；After reaction, it then is post-processed and obtains 2- chloro benzothiazole.
The proportion of material: the molar ratio of benzothiazole and atent solvent is 1:0.1 ~ 10；Mole of benzothiazole and chlorine
Than for 1:0.2 ~ 2, the molar ratio of catalyst and benzothiazole is 1:10 ~ 200.
Atent solvent is one or more of monochlor-benzene, o-dichlorohenzene, dichloroethanes, chloroform, trichloro-benzenes.
Catalyst be phosphorus trichloride, phosphorus pentachloride, one of thionyl chloride, chlorosulfuric acid, alchlor, ferric trichloride or
It is several.
Chlorination reaction temperature is 60 ~ 160 DEG C.
The post-processing is used in combination using crystallization, vacuum distillation or both；Crystallization temperature: -5 ~ 20 DEG C, vacuum distillation temperature
Degree: 120 ~ 160 DEG C, vacuum degree: 0.095 ~ 0.099Mpa.
Chlorinated exhaust processing after reaction: hydrochloric acid is first absorbed to obtain with water, then absorbs to obtain liquor natrii hypochloritis with lye.
By-product when the raw materials used in the present invention benzothiazole can be by production 2-mercaptobenzothiazole is isolated to；It can also
It directly synthesizes to obtain by aniline and formaldehyde, sulphur.It is easy to get with raw material, simple process, easy to operate, reaction condition is mild, molten
The features such as agent recoverable, yield is higher, high-quality, is suitble to industrialized production；Production cost is reduced, the dirt to environment is reduced
Dye.
Below with reference to embodiment, the invention will be further described.
Specific embodiment
Embodiment 1:
Cooler and chlorine hydride tail gas absorber are being had, can be stirred and the 500ml reaction for having chlorine ingress pipe is burnt
In bottle, 150g benzothiazole, 150g chlorobenzene and 3g phosphorus trichloride catalyst are thrown, is warming up to 80 DEG C, is started with (1~2) g/min
It is passed through chlorine, reaction maintains (120~150) DEG C.Insulation reaction detects that the benzothiazole content in system is lower than to HPLC
Stop logical chlorine when 0.5%, leads to about 80 grams of chlorine dose.It is rushed extra chlorine, the as chlorine of 2- chloro benzothiazole with nitrogen after reaction
Benzole soln.By vacuum distillation, deviates from chlorobenzene and a small amount of raw material lower batch is applied, surplus material filters to obtain 2- chlorine through decrease temperature crystalline
175 grams of benzothiazole, content 98%, yield 91%.The chlorobenzene solution of recycling and filtered mother liquor, lower batch is applied.
Cooler and chlorine hydride tail gas absorber are being had, can be stirred and the 500ml for having chlorine ingress pipe is anti-
It answers in flask, throws 150g benzothiazole, upper batch of recycling chlorobenzene and filtrated stock and 1.5g phosphorus trichloride catalyst, be warming up to 80
DEG C, start to be passed through chlorine with (1~2) g/min, reaction maintains (120~150) DEG C, and insulation reaction to HPLC detects system
In benzothiazole content stop logical chlorine when being lower than 0.5%, lead to chlorine dose about 82g.Extra chlorine is rushed i.e. with nitrogen after reaction
For the chlorobenzene solution of 2- chloro benzothiazole.By vacuum distillation, deviate from chlorobenzene and a small amount of raw material.Surplus material through decrease temperature crystalline,
Filter to obtain 2- chloro benzothiazole 182g, content 98.2%, yield 95%.Filtered mother liquor obtains 2- chlorine through vacuum distillation recycling
Benzothiazole 2.26g, content 99%.Total recovery 96%.The chlorobenzene solution of recycling can continue to apply.
Embodiment 2:
Cooler and chlorine hydride tail gas absorber are being had, can be stirred and the 500ml reaction for having chlorine ingress pipe is burnt
In bottle, 150g benzothiazole, 160g o-dichlorohenzene and 3g phosphorus trichloride catalyst are thrown, is warming up to 80 DEG C, is started with (1~2) g/
Min is passed through chlorine, and reaction maintains (100~130) DEG C insulation reaction and detects that the benzothiazole content in system is low to HPLC
Stop logical chlorine when 0.5%, leads to chlorine dose about 85g.It is rushed extra chlorine with nitrogen after reaction, as 2- chloro benzothiazole is adjacent
Dichlorobenzene solution.Lower batch of reuse is supplied by vacuum distillation abjection o-dichlorohenzene and a small amount of raw material.Surplus material is through decrease temperature crystalline, mistake
Filter to obtain 2- chloro benzothiazole, 174g, content 98.1%.Yield 90%.The mother liquor being obtained by filtration and the o-dichlorobenzene solution of recycling one
It removes to criticize and apply.
Cooler and chlorine hydride tail gas absorber are being had, can be stirred and the 500ml for having chlorine ingress pipe is anti-
It answers in flask, throws 150g benzothiazole, upper batch of recycling o-dichlorohenzene and filtrated stock and 1.5g phosphorus trichloride catalyst, heating
To 80 DEG C, start to be passed through chlorine with (1~2) g/min, reaction maintains (100~130) DEG C insulation reaction and detects to HPLC
Benzothiazole content in system stops logical chlorine when being lower than 0.5%, lead to chlorine dose about 85g.Nitrogen is rushed extra chlorine after reaction
Gas, the as o-dichlorobenzene solution of 2- chloro benzothiazole.By vacuum distillation abjection o-dichlorohenzene and a small amount of raw material, covered for lower batch
With.Surplus material filters to obtain 2- chloro benzothiazole 183g, content 98.1% through decrease temperature crystalline.Yield 95%.Filtered mother liquor warp
Vacuum distillation recycling obtains 2- chloro benzothiazole 1.86g, content 99%.Total recovery 96.2%.The o-dichlorobenzene solution of recycling can be after
It is continuous to apply.
Embodiment 3:
It is burnt with cooler and chlorine hydride tail gas absorber, the 1000ml that can be stirred and have chlorine ingress pipe reaction
In bottle, 300g benzothiazole, 300g dichloroethanes and 5g phosphorus pentachloride catalyst are thrown, is warming up to 80 DEG C, is started with (2~3) g/
Min is passed through chlorine, and rear maintaining reaction temperature is in (90~120) DEG C and continues logical chlorine.The benzo thiophene in system is detected to HPLC
Azoles content stops logical chlorine when being lower than 0.5%, claim to obtain logical chlorine dose about 165g.It is rushed extra chlorine with nitrogen after reaction, obtains 2-
Chloro benzothiazole dichloroethane solution.By vacuum distillation, deviates from dichloroethanes and a small amount of raw material and applied for lower batch.Surplus material
Through decrease temperature crystalline, 2- chloro benzothiazole 352g, content 98.2% are filtered to obtain.91 % of yield.Filtrated stock lower batch is applied.
Cooler and chlorine hydride tail gas absorber are being had, can be stirred and the 1000ml for having chlorine ingress pipe is anti-
It answers in flask, throws 300g benzothiazole, upper batch of recycling dichloroethane solution and the catalysis of filtrated stock 310g and 1.5g phosphorus pentachloride
Agent is warming up to 80 DEG C, is passed through chlorine with (2~3) g/min speed, temperature maintains (90~120) DEG C, until HPLC detects body
Benzothiazole content in system stops logical chlorine when being lower than 0.5%, claim to obtain logical chlorine dose about 162g.Nitrogen is rushed extra after reaction
Chlorine, solution are 2- chloro benzothiazole.By vacuum distillation, deviates from dichloroethanes and a small amount of raw material and applied for lower batch.It is remaining
Material filters to obtain 2- chloro benzothiazole, 361g, content 98.3% through decrease temperature crystalline.Yield 94.8%.Filtered mother liquor vacuum is steamed
It evaporates recycling and obtains 2- chloro benzothiazole 4.52g, content 99%.Total recovery 95.5%.The dichloroethane Soluble liquid of recycling continues to apply.
Embodiment 4:
Cooler and chlorine hydride tail gas absorber are being had, can be stirred and the 2000ml reaction for having chlorine ingress pipe is burnt
In bottle, 600g benzothiazole, 500g chlorobenzene and 10g phosphorus oxychloride catalyst are thrown, is warming up to 80 DEG C, is started with (3~5) g/min
It is passed through chlorine, reaction maintains (80~100) DEG C insulation reaction and detects that the benzothiazole content in system is lower than to HPLC
Stop logical chlorine when 0.5%, leads to about 300 grams of chlorine dose.Nitrogen is rushed extra chlorine, as 2- chloro benzothiazole chlorobenzene after reaction
Solution.By vacuum distillation, deviates from chlorobenzene and a small amount of raw material and applied for lower batch.Surplus material is steamed through condition of high vacuum degree 0.099mpa
It evaporates to 165 DEG C, obtains 2- chloro benzothiazole, 725g, content 99%.Yield 95.3%.
Embodiment 5:
Cooler and chlorine hydride tail gas absorber are being had, can be stirred and the 500ml reaction for having chlorine ingress pipe is burnt
In bottle, 150g benzothiazole, 170g chlorobenzene and 2g thionyl chloride catalysis agent are thrown, is warming up to 80 DEG C, is started with (1~2) g/min
Speed is passed through chlorine, and reaction maintains (90~110) DEG C insulation reaction and detects that the benzothiazole content in system is low to HPLC
Stop logical chlorine when 0.5%, leads to about 75 grams of chlorine dose.Nitrogen is rushed extra chlorine, as 2- chloro benzothiazole chlorobenzene after reaction
Solution.By vacuum distillation, deviates from chlorobenzene and a small amount of raw material and applied for lower batch.Surplus material is steamed through condition of high vacuum degree 0.099mpa
It evaporates to 165 DEG C, obtains 2- chloro benzothiazole, 180g, content 98.5%.Yield 94.03%.
Above embodiment only technology and feature to illustrate the invention, its object is to allow person skilled in the art's energy
The solution contents of the present invention much of that are simultaneously implemented accordingly, and it is not intended to limit the scope of the present invention.It is all spiritual according to the present invention
The equivalent transformation or modification that essence is done, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of synthetic method of 2- chloro benzothiazole, it is characterised in that: synthesize 2- chlorine through chlorine direct chlorination by benzothiazole
Benzothiazole；Specifically includes the following steps: the atent solvent of metering and benzothiazole, catalyst to be added and have cooler and tail
It in aspiration receiving apparatus, the reactor that can be stirred and have chlorine ingress pipe, heats up, the chlorine for starting to be continually fed into metering is anti-
It answers；After reaction, it then is post-processed and obtains 2- chloro benzothiazole.
2. a kind of synthetic method of 2- chloro benzothiazole according to claim 1, it is characterised in that: the proportion of material: benzene
And the molar ratio of thiazole and atent solvent is 1:0.1 ~ 10；The molar ratio of benzothiazole and chlorine is 1:0.2 ~ 2, catalyst and benzene
And the molar ratio of thiazole is 1:10 ~ 200.
3. a kind of synthetic method of 2- chloro benzothiazole according to claim 1, it is characterised in that: atent solvent is a chlorine
For one or more of benzene, o-dichlorohenzene, dichloroethanes, chloroform, trichloro-benzenes.
4. a kind of synthetic method of 2- chloro benzothiazole according to claim 1, it is characterised in that: catalyst is tri-chlorination
Phosphorus, phosphorus pentachloride, one or more of thionyl chloride, chlorosulfuric acid, alchlor, ferric trichloride.
5. a kind of synthetic method of 2- chloro benzothiazole according to claim 1, it is characterised in that: chlorination reaction temperature is
60~160℃。
6. a kind of synthetic method of 2- chloro benzothiazole according to claim 1, it is characterised in that: the post-processing is
It is used in combination using crystallization, vacuum distillation or both；Crystallization temperature: -5 ~ 20 DEG C, vacuum distillation temperature: 120 ~ 160 DEG C, vacuum degree:
0.095~0.099Mpa。
7. a kind of synthetic method of 2- chloro benzothiazole according to claim 1, it is characterised in that: the chlorination tail after reaction
Gas disposal: hydrochloric acid is first absorbed to obtain with water, then absorbs to obtain liquor natrii hypochloritis with lye.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS213291B1 (en) * | 1981-01-23 | 1982-04-09 | Josef Hromas | Method of making the 2-chlorbenzthiazole |
| DE3234530A1 (en) * | 1982-09-17 | 1984-03-22 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING 2-CHLORBENZTHIAZOL |
| US6274739B1 (en) * | 1997-12-16 | 2001-08-14 | Aventis Cropscience Gmbh | Method for producing chlorobenzoxazolene |
| CN105198834A (en) * | 2015-09-23 | 2015-12-30 | 上海泰坦科技股份有限公司 | Synthesizing process of 2, 6-dibromo benzothiazole |
| CN107033102A (en) * | 2017-05-02 | 2017-08-11 | 江苏永凯化学有限公司 | The synthetic method of mefenacet |
| CN107129484A (en) * | 2017-06-05 | 2017-09-05 | 江苏永凯化学有限公司 | The synthetic method of 2 chloro benzothiazoles |
-
2019
- 2019-01-11 CN CN201910024834.9A patent/CN109456282A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS213291B1 (en) * | 1981-01-23 | 1982-04-09 | Josef Hromas | Method of making the 2-chlorbenzthiazole |
| DE3234530A1 (en) * | 1982-09-17 | 1984-03-22 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING 2-CHLORBENZTHIAZOL |
| US6274739B1 (en) * | 1997-12-16 | 2001-08-14 | Aventis Cropscience Gmbh | Method for producing chlorobenzoxazolene |
| CN105198834A (en) * | 2015-09-23 | 2015-12-30 | 上海泰坦科技股份有限公司 | Synthesizing process of 2, 6-dibromo benzothiazole |
| CN107033102A (en) * | 2017-05-02 | 2017-08-11 | 江苏永凯化学有限公司 | The synthetic method of mefenacet |
| CN107129484A (en) * | 2017-06-05 | 2017-09-05 | 江苏永凯化学有限公司 | The synthetic method of 2 chloro benzothiazoles |
Non-Patent Citations (1)
| Title |
|---|
| 庞怀林等: "除草剂苯噻草胺的合成", 《湖南化工》 * |
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