CN105418470B - A kind of synthetic method of clethodim - Google Patents
A kind of synthetic method of clethodim Download PDFInfo
- Publication number
- CN105418470B CN105418470B CN201510787549.4A CN201510787549A CN105418470B CN 105418470 B CN105418470 B CN 105418470B CN 201510787549 A CN201510787549 A CN 201510787549A CN 105418470 B CN105418470 B CN 105418470B
- Authority
- CN
- China
- Prior art keywords
- reaction
- toluene
- kettle
- warming
- stirring
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of synthetic method of clethodim, this patent are related to cyclohexenone analog herbicide clethodim, i.e. (±) 2 [(E) 3 chloroallyloxyamino imino group] propyl group 5 [2（Ethylmercapto group）Propyl group] 3 hydroxy cyclohexylphenyl, 2 ketenes.This product generates clethodim as primary raw material and micro catalyst using ethyl mercaptan and crotonaldehyde, ethyl acetoacetate, ethylmercapto group heptenone, propionyl chloride by chain reaction.Technique of the invention is green, high financial profit.
Description
Technical field
The present invention relates to cyclohexenone analog herbicide clethodim, i.e. (±) -2- [(E) -3- chloroallyloxyaminos imino group]
Propyl group -5- [2-（Ethylmercapto group）Propyl group] -3- hydroxy cyclohexylphenyl -2- ketenes synthesis technique.
Background technology
The technique of conventional synthesis clethodim is to use Witting reagents, is completed by Witting reactions, yield is
95% .Witting reagent prices costliness, cost in this method is high, and the hydrogen phosphide for reacting generation is difficult to handle.
The content of the invention
It is for this technical solution adopted by the present invention：The present invention is carried out according to the following steps：
1）Ethyl mercaptan and crotonaldehyde are added first in addition reaction kettle, is stirred, addition reaction is carried out under normal temperature and pressure；With
Add ethyl acetoacetate and alkali lye in a kettle afterwards, stirring is warming up to 60-80 DEG C, is incubated 8-12h under normal pressure, obtains ethylmercapto group
Heptenone, reaction add the mixed liquor of toluene and water, stratification after terminating, waste water is discharged into Waste Water Treatment, and organic layer turns
Enter ring-closure reaction kettle；
2）Diethyl malonate and caustic alcohol are added in ring-closure reaction kettle, stirring is warming up to 90-120 DEG C, is returned in toluene
5-7h is reacted under stream mode, obtains cyclocomplex；The ethanol of reaction generation is reclaimed after B-grade condensation, and on-condensible gas is arranged by aiutage
Put；Ring-closure reaction is cooled to 35-50 DEG C after terminating, add propionyl chloride in a kettle and carry out esterification；
3）After esterification terminates, reaction is transferred to Basic fluxing raction kettle, adds alkali and water, stirring is warming up to 70-90 DEG C, instead
Should about 4.5-6h, after Basic fluxing raction terminates, stratification, toluene uses by distillation, closed condensation recovery toluene Posterior circle, residual
Slag burning disposal, a small amount of on-condensible gas are discharged after using charcoal absorption by high aiutage, and water layer is sent into decarboxylation kettle, are added
Appropriate hydrochloric acid, stirring are warming up to 90-120 DEG C, synthesis under normal pressure 5-7h, add toluene solvant and carry out stratification, waste water is discharged into place
Reason station, toluene layer are transferred to translocation reaction kettle；
4）In translocation reaction kettle, catalyst dimethylamino pyridine is added, stirring is warming up to 100-110 DEG C, is returned in toluene
React 9-12h under stream mode, indexing is attained the Way the third 3 ketone, and reaction is cooled to 25-35 DEG C after terminating, added in a kettle
Allyl oxygen amine carries out condensation reaction, obtains clethodim crude product；Then stratification is carried out, waste water is discharged into Waste Water Treatment, first
Benzene layer obtains finished product clethodim after distillation, sealed condensating recovery toluene, and a small amount of on-condensible gas leads to after charcoal absorption
Too high aiutage discharge.
It is an advantage of the invention that：1）The present invention is with ethyl mercaptan and crotonaldehyde, ethyl acetoacetate, ethylmercapto group heptenone, third
Acyl chlorides is main Material synthesis clethodim, is used in course of reaction to self-control catalyst, and it is chain reaction to react, operation letter
It is single；
2）The quantity of solvent that uses of present invention reaction is few, reacts that the catalytic amount used is few, reacts the solvent toluene energy used
Enough recycle；
3）Waste gas caused by the present invention can be effectively addressed：（1）Rectifying column in reaction, which produces, does not coagulate exhaust emissions,
Composition is ethanol；（2）Rectifying column, which produces, in reaction does not coagulate exhaust emissions, and composition is toluene；（3）Reaction produces carbon dioxide
Discharge；（4）Reactive distillation column, which produces, does not coagulate exhaust emissions, and composition is that toluene can be recycled utilization.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Specific embodiment
Embodiment one
The present invention adds quantitative ethyl mercaptan and crotonaldehyde in addition reaction kettle first, stirs, and is carried out under normal temperature and pressure
Addition reaction；Quantitative ethyl acetoacetate and alkali lye are then added in a kettle, and stirring is warming up to 70 DEG C, is incubated under normal pressure
10h, ethylmercapto group heptenone is obtained, reaction adds the mixed liquor of toluene and water, stratification after terminating, waste water is discharged into wastewater treatment system
System, organic layer are transferred to ring-closure reaction kettle.
Appropriate diethyl malonate and caustic alcohol are added in ring-closure reaction kettle, stirring is warming up to 100 DEG C or so, in toluene
About 6h is reacted under reflux state, obtains cyclocomplex.The ethanol of reaction generation reclaims after B-grade condensation, and on-condensible gas passes through aiutage
Discharge.Ring-closure reaction is cooled to 40 DEG C or so after terminating, add appropriate propionyl chloride in a kettle and carry out esterification.
After esterification terminates, reaction is transferred to Basic fluxing raction kettle, adds alkali and water, stirring is warming up to 80 DEG C, and reaction is about
5h, after Basic fluxing raction terminates, stratification, toluene uses by distillation, closed condensation recovery toluene Posterior circle, at burning residual dregs
Reason, a small amount of on-condensible gas are discharged after using charcoal absorption by 15 meters high aiutage, and water layer is sent into decarboxylation kettle, are added appropriate
Hydrochloric acid, stirring are warming up to 100 DEG C, synthesis under normal pressure about 6h, add toluene solvant and carry out stratification, waste water is discharged into treating stations, first
Benzene layer is transferred to translocation reaction kettle.
In translocation reaction kettle, catalyst is added（Dimethylamino pyridine）, stirring is warming up to 100-110 DEG C, in toluene time
React 10h under stream mode, indexing is attained the Way the third 3 ketone, and reaction is cooled to 30 DEG C after terminating, added in a kettle quantitative
Allyl oxygen amine carries out condensation reaction, obtains clethodim crude product.Then stratification is carried out, waste water is discharged into Waste Water Treatment, first
Benzene layer obtains finished product clethodim after distillation, sealed condensating recovery toluene, and a small amount of on-condensible gas leads to after charcoal absorption
Cross 15 meters high aiutage discharge.
Embodiment two
1）Ethyl mercaptan and crotonaldehyde are added first in addition reaction kettle, is stirred, addition reaction is carried out under normal temperature and pressure；With
Add ethyl acetoacetate and alkali lye in a kettle afterwards, stirring is warming up to 70 DEG C, is incubated 11h under normal pressure, obtains ethylmercapto group heptene
Ketone, reaction add the mixed liquor of toluene and water, stratification after terminating, waste water is discharged into Waste Water Treatment, and organic layer, which is transferred to, to be closed
Ring reactor；
2）Diethyl malonate and caustic alcohol are added in ring-closure reaction kettle, stirring is warming up to 90 DEG C, in refluxing toluene shape
7h is reacted under state, obtains cyclocomplex；The ethanol of reaction generation reclaims after B-grade condensation, and on-condensible gas discharges by aiutage；Close
Ring reaction is cooled to 35 DEG C after terminating, and adds propionyl chloride in a kettle and carries out esterification；
3）After esterification terminates, reaction is transferred to Basic fluxing raction kettle, adds alkali and water, stirring is warming up to 80 DEG C, reaction
About 5h, after Basic fluxing raction terminates, stratification, toluene uses by distillation, closed condensation recovery toluene Posterior circle, burning residual dregs
Processing, a small amount of on-condensible gas are discharged after using charcoal absorption by high aiutage, and water layer is sent into decarboxylation kettle, adds appropriate salt
Acid, stirring are warming up to 120 DEG C, synthesis under normal pressure 5.5h, add toluene solvant and carry out stratification, waste water is discharged into treating stations, toluene
Layer is transferred to translocation reaction kettle；
4）In translocation reaction kettle, catalyst dimethylamino pyridine is added, stirring is warming up to 100 DEG C, in refluxing toluene shape
React 10h under state, indexing is attained the Way the third 3 ketone, and reaction is cooled to 30 DEG C after terminating, adds allyl oxygen amine in a kettle
Condensation reaction is carried out, obtains clethodim crude product；Then stratification is carried out, waste water is discharged into Waste Water Treatment, and toluene layer passes through
Finished product clethodim is obtained after distillation, sealed condensating recovery toluene, a small amount of on-condensible gas is vented after charcoal absorption by height
Cylinder discharge.
Embodiment three
The present invention is carried out according to the following steps：
1）Ethyl mercaptan and crotonaldehyde are added first in addition reaction kettle, is stirred, addition reaction is carried out under normal temperature and pressure；With
Add ethyl acetoacetate and alkali lye in a kettle afterwards, stirring is warming up to 60 DEG C, is incubated 12h under normal pressure, obtains ethylmercapto group heptene
Ketone, reaction add the mixed liquor of toluene and water, stratification after terminating, waste water is discharged into Waste Water Treatment, and organic layer, which is transferred to, to be closed
Ring reactor；
2）Diethyl malonate and caustic alcohol are added in ring-closure reaction kettle, stirring is warming up to 105 DEG C, in refluxing toluene shape
7h is reacted under state, obtains cyclocomplex；The ethanol of reaction generation reclaims after B-grade condensation, and on-condensible gas discharges by aiutage；Close
Ring reaction is cooled to 40 DEG C after terminating, and adds propionyl chloride in a kettle and carries out esterification；
3）After esterification terminates, reaction is transferred to Basic fluxing raction kettle, adds alkali and water, stirring is warming up to 90 DEG C, reaction
About 6h, after Basic fluxing raction terminates, stratification, toluene uses by distillation, closed condensation recovery toluene Posterior circle, burning residual dregs
Processing, a small amount of on-condensible gas are discharged after using charcoal absorption by high aiutage, and water layer is sent into decarboxylation kettle, adds appropriate salt
Acid, stirring are warming up to 105 DEG C, synthesis under normal pressure 5h, add toluene solvant and carry out stratification, waste water is discharged into treating stations, toluene layer
It is transferred to translocation reaction kettle；
4）In translocation reaction kettle, catalyst dimethylamino pyridine is added, stirring is warming up to 105 DEG C, in refluxing toluene shape
React 9h under state, indexing is attained the Way the third 3 ketone, and reaction is cooled to 35 DEG C after terminating, adds allyl oxygen amine in a kettle and enter
Row condensation reaction, obtain clethodim crude product；Then stratification is carried out, waste water is discharged into Waste Water Treatment, and toluene layer is by steaming
Evaporate, obtain finished product clethodim after sealed condensating recovery toluene, a small amount of on-condensible gas passes through high aiutage after charcoal absorption
Discharge.
Example IV
The present invention follows the steps below：
1）Ethyl mercaptan and crotonaldehyde are added first in addition reaction kettle, is stirred, addition reaction is carried out under normal temperature and pressure；With
Add ethyl acetoacetate and alkali lye in a kettle afterwards, stirring is warming up to 60 DEG C, is incubated 9h under normal pressure, obtains ethylmercapto group heptene
Ketone, reaction add the mixed liquor of toluene and water, stratification after terminating, waste water is discharged into Waste Water Treatment, and organic layer, which is transferred to, to be closed
Ring reactor；
2）Diethyl malonate and caustic alcohol are added in ring-closure reaction kettle, stirring is warming up to 95 DEG C, in refluxing toluene shape
6.5h is reacted under state, obtains cyclocomplex；The ethanol of reaction generation reclaims after B-grade condensation, and on-condensible gas discharges by aiutage；
Ring-closure reaction is cooled to 45 DEG C after terminating, add propionyl chloride in a kettle and carry out esterification；
3）After esterification terminates, reaction is transferred to Basic fluxing raction kettle, adds alkali and water, stirring is warming up to 90 DEG C, reaction
About 5.2h, after Basic fluxing raction terminates, stratification, toluene uses by distillation, closed condensation recovery toluene Posterior circle, and residue burns
Burning processing, a small amount of on-condensible gas are discharged after using charcoal absorption by high aiutage, and water layer is sent into decarboxylation kettle, are added appropriate
Hydrochloric acid, stirring are warming up to 115 DEG C, synthesis under normal pressure 7h, add toluene solvant and carry out stratification, waste water is discharged into treating stations, toluene
Layer is transferred to translocation reaction kettle；
4）In translocation reaction kettle, catalyst dimethylamino pyridine is added, stirring is warming up to 105 DEG C, in refluxing toluene shape
React 11.5h under state, indexing is attained the Way the third 3 ketone, and reaction is cooled to 25 DEG C after terminating, adds allyl oxygen in a kettle
Amine carries out condensation reaction, obtains clethodim crude product；Then stratification is carried out, waste water is discharged into Waste Water Treatment, toluene layer warp
Finished product clethodim is obtained after crossing distillation, sealed condensating recovery toluene, a small amount of on-condensible gas is arranged after charcoal absorption by height
Inflator discharges.
Claims (1)
1. a kind of synthetic method of clethodim, it is characterised in that carry out according to the following steps：
1）Ethyl mercaptan and crotonaldehyde are added first in addition reaction kettle, is stirred, addition reaction is carried out under normal temperature and pressure；Then exist
Ethyl acetoacetate and alkali lye are added in reactor, stirring is warming up to 60-80 DEG C, is incubated 8-12h under normal pressure, obtains ethylmercapto group heptene
Ketone, reaction add the mixed liquor of toluene and water, stratification after terminating, waste water is discharged into Waste Water Treatment, and organic layer, which is transferred to, to be closed
Ring reactor；
2）Diethyl malonate and caustic alcohol are added in ring-closure reaction kettle, stirring is warming up to 90-120 DEG C, in refluxing toluene shape
5-7h is reacted under state, obtains cyclocomplex；The ethanol of reaction generation reclaims after B-grade condensation, and on-condensible gas discharges by aiutage；
Ring-closure reaction is cooled to 35-50 DEG C after terminating, add propionyl chloride in a kettle and carry out esterification；
3）After esterification terminates, reaction is transferred to Basic fluxing raction kettle, adds alkali and water, stirring is warming up to 70-90 DEG C, reaction
4.5-6h, after Basic fluxing raction terminates, stratification, toluene uses by distillation, closed condensation recovery toluene Posterior circle, and residue burns
Burning processing, a small amount of on-condensible gas are discharged after using charcoal absorption by high aiutage, and water layer is sent into decarboxylation kettle, are added appropriate
Hydrochloric acid, stirring are warming up to 90-120 DEG C, synthesis under normal pressure 5-7h, add toluene solvant and carry out stratification, and waste water is discharged into treating stations,
Toluene layer is transferred to translocation reaction kettle；
4）In translocation reaction kettle, catalyst dimethylamino naphthyridine is added, stirring is warming up to 100-110 DEG C, in refluxing toluene shape
9-12h is reacted under state, indexing obtains the third 3 ketone, and reaction is cooled to 25-35 DEG C after terminating, and adds 3- chlorine in a kettle
Allyl oxygen amine carries out condensation reaction, obtains clethodim crude product；Then stratification is carried out, waste water is discharged into Waste Water Treatment, first
Benzene layer obtains finished product clethodim after distillation, sealed condensating recovery toluene, and a small amount of on-condensible gas leads to after charcoal absorption
Too high aiutage discharge；
Described 3）The toluene reclaimed in step is recycled to 1）It is used in step as de-laminating solvent, described 4）The toluene of step recovery
It is recycled to 3）Solvent in step as translocation reaction is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510787549.4A CN105418470B (en) | 2015-11-17 | 2015-11-17 | A kind of synthetic method of clethodim |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510787549.4A CN105418470B (en) | 2015-11-17 | 2015-11-17 | A kind of synthetic method of clethodim |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105418470A CN105418470A (en) | 2016-03-23 |
| CN105418470B true CN105418470B (en) | 2017-12-15 |
Family
ID=55497076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510787549.4A Active CN105418470B (en) | 2015-11-17 | 2015-11-17 | A kind of synthetic method of clethodim |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105418470B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187841B (en) * | 2016-07-08 | 2018-01-30 | 山东润博生物科技有限公司 | A kind of industrialized process for preparing of clethodim |
| CN106748673B (en) * | 2016-11-21 | 2020-05-19 | 潍坊先达化工有限公司 | Preparation method of 5- {2- (ethylthio) propyl } -3-hydroxy-cyclohex-2-enone |
| CN107029636B (en) * | 2017-05-25 | 2023-10-20 | 潍坊先达化工有限公司 | Production method and device of 3-ethylthio butyraldehyde |
| CN111978220A (en) * | 2020-08-10 | 2020-11-24 | 宁夏一帆生物科技有限公司 | Method for synthesizing clethodim crude drug |
| CN111892520B (en) * | 2020-08-28 | 2022-06-14 | 山东潍坊润丰化工股份有限公司 | Environment-friendly synthesis method of clethodim |
| CN112500322A (en) * | 2020-12-01 | 2021-03-16 | 安道麦安邦(江苏)有限公司 | Production method of clethodim preparation |
| CN115286500A (en) * | 2022-08-31 | 2022-11-04 | 山东新和成氨基酸有限公司 | Preparation method and composition of acetoacetic acid, 6-ethylthio-3-heptylene-2-ketone and intermediate thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR920010518B1 (en) * | 1985-08-23 | 1992-12-04 | 세브런 리써취 캄파니 | 2-|1-(3-chloroallyloxamino) alkylidene¨-5-alkyl thio alkyl-cychohexane-1,3-dione herbicides |
| US6300281B1 (en) * | 2000-07-03 | 2001-10-09 | Valent U.S.A. Corporation | Optically pure(−) clethodim, compositions and methods for controlling plant growth comprising the same |
-
2015
- 2015-11-17 CN CN201510787549.4A patent/CN105418470B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105418470A (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105418470B (en) | A kind of synthetic method of clethodim | |
| CN103787874B (en) | A kind of preparation technology of Benzoyl chloride | |
| WO2021129377A1 (en) | Method for treating byproduct hydrogen chloride in fluorine-containing olefin production process | |
| CN108586423A (en) | A kind of production technology of novel chlorocarbonic acid vinyl acetate | |
| CN102351684B (en) | Preparation method of 2-phenylpropionic acid | |
| CN102372610B (en) | Extraction and rectification technology and preparation apparatus of high-density methylal | |
| CN104383949B (en) | A kind of Ketocyclopentane catalyst for synthesizing and preparation method thereof and the application in Ketocyclopentane synthesizes | |
| CN109879728A (en) | A kind of method of catalysis of phenol and methanol-fueled CLC methyl phenyl ethers anisole | |
| CN102584696B (en) | Catalytic synthesis method for rubber antioxidant RD | |
| CN107501035A (en) | A kind of production method of Benzene Chloride | |
| CN101786947A (en) | Method for preparing benzaldehyde by oxidizing toluene | |
| CN109053461A (en) | A kind of method that neighbour's chlorine para-nitrotoluene catalytic hydrogenation synthesizes adjacent chlorine para-aminotoluene | |
| CN110180524A (en) | A method of carbonic acid glyceride is prepared based on calcium silicates based composite catalyst | |
| CN109608306A (en) | A kind of industrialized preparing process and process units of 2,5- dimethyl -2,5-HD | |
| CN101693660B (en) | Tubular continuous method for preparing cyclopropanecarboxylic acid | |
| CN103772153B (en) | The synthetic method of the chloro-3-cresols of 4-and system thereof | |
| CN107597173A (en) | A kind of catalyst of phenol hydroxylation synthesizing benzene diphenol and preparation method thereof | |
| CN111393273B (en) | System and method for preparing benzaldehyde from PTA oxidation residues | |
| CN109651072B (en) | Method for preparing chloroethane from hydrochloric acid containing sulfur dioxide | |
| CN106478422A (en) | A kind of preparation method of paranitrophenylacetic acid | |
| CN106944112B (en) | Pre-esterification solid acid catalyst for high-acid-value waste oil | |
| CN111187138A (en) | Method for treating dichlorobenzene rectification residue | |
| CN102443123B (en) | Comprehensive utilization method of hydrogenated dimethylbenzene | |
| CN106478360B (en) | The catalytic chlorination system of methylene chloride yield ratio can be improved | |
| CN107445793A (en) | A kind of distillation and separation method of benzene chloride production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |