CN106187841B - A kind of industrialized process for preparing of clethodim - Google Patents
A kind of industrialized process for preparing of clethodim Download PDFInfo
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- CN106187841B CN106187841B CN201610533417.3A CN201610533417A CN106187841B CN 106187841 B CN106187841 B CN 106187841B CN 201610533417 A CN201610533417 A CN 201610533417A CN 106187841 B CN106187841 B CN 106187841B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
- C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
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Abstract
The invention discloses a kind of industrialized process for preparing of clethodim, and using dichloromethane as solvent, the cyclohexanedione of 5 [2 (ethylmercapto group) propyl group] 2 propiono 1,3 and chloroallyl oxygen amine are carried out into reaction generation clethodim.The present invention is replaced to solvent, can also reacted in the case of being added without catalyst at a temperature of 20 25 DEG C, is saving energy resource consumption, reduce the decomposition of clethodim, avoid the introducing of additional impurities, improve product yield and content.
Description
Technical field
The present invention relates to a kind of preparation method of clethodim, and in particular to the low clethodim of a kind of mild condition, cost
Industrialized process for preparing, belong to clethodim preparing technical field.
Background technology
Clethodim, English name clethodim, alias receive happy logical, seroxat, chemical name：（±）- 2-（E）- 3- chlorine alkene
Propoxyl group imino group ］ propyl group -5- [2- ethylsuleenyl propyls] -3- hydroxyl -2- cyclohexene -1- ketone, belong to cyclonene
Class herbicide.Clethodim is the cyclohexenone analog herbicide developed by Chevron chemical companies of the U.S. nineteen eighty-two, and the medicine is interior
Conduction type high selectivity post-emergence herbicide is inhaled, to broad leaf crop safety, available for a variety of dicotyledonous works such as soybean, cotton, rape
The annual and perennial grassy weed such as thing field, effective Control Wild oat, Brachiaria Griseb, black bromegrass, lady's-grass, green bristlegrass.
The trade name that Chevron chemical companies of the U.S. use is received happy logical medicine and used in China for many years, and the product removes
Careless effect is fine always, receives the trust and welcome of vast farmerses, is a kind of important active material in pesticide field, has
Have high-efficiency broad spectrum bioactivity and it is environmentally friendly many advantages, such as, it has also become the new lover in market, market prospects are extremely wide.
At present, industrially the preparation method of conventional clethodim is：（1）Using crotonaldehyde, ethyl mercaptan as raw material, triethylamine is done
Catalyst synthesizes 3- ethylmercapto group butyraldehyde；（2）Using ethyl acetoacetate, liquid caustic soda as raw material, water is solvent synthesis of acetyl acetic acid sodium salt；
（3）Using 3- ethylmercapto groups butyraldehyde, acetoacetate sodium salt makees solvent as raw material, toluene, piperidines makees catalyst, pH in acetic acid regulation reaction
Value synthesis 6- ethylmercapto groups -3- alkene -2-HEPTANONE；（4）6- ethylmercapto groups -3- alkene -2-HEPTANONE-toluene solution is with diethyl malonate in first
Cyclization reaction is carried out in the presence of sodium alkoxide, propionyl chloride is added after dealcoholysis and is acylated, PDM（That is DMAP）Catalytically rearranging, then through liquid caustic soda water
Solution, salt acid decarboxylation, petroleum ether extraction generation 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, hydroresorcinol, slough petroleum ether
After obtain 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, hydroresorcinol crude product, then fine work 5- is obtained after high vacuum distillation
[2- (ethylmercapto group) propyl group] -2- propionos-hydroresorcinol；（5）Fine work 5- [2- (ethylmercapto group) propyl group] -2- propiono -1,
Hydroresorcinol generates clethodim with chloroallyl oxygen amine by solvent reaction of petroleum ether.Each step reaction equation is as follows：
In conventional method, with 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, hydroresorcinol and chloroallyl oxygen amine
Concretely comprising the following steps for clethodim is prepared for raw material：5- [2- (ethylmercapto group) propyl group] -2- propionos-hydroresorcinol is added into stone
In oily ether, keeping temperature is 55-60 DEG C after stirring, then adds chloroallyl oxygen amine, maintains the temperature at 55-60 DEG C and carries out instead
Should, 5- [2- (ethylmercapto group) propyl group] -2- propiono -1 is detected, reacts and terminates when hydroresorcinol content is less than 0.5%, Ran Houyong
Sour water is washed, the vacuum distillation at 60-80 DEG C, is deviate from aqueous solvent, is obtained clethodim.Clethodim technical pesticide activity is high, easily drops
Solution, it is especially temperature sensitive, just there is more obvious decomposition when temperature is higher than 20 DEG C, therefore, under existing reaction temperature, instead
Just there is portioned product to start to decompose when should carry out, if reducing reaction temperature, need the addition of catalyst, but add catalysis
Agent can introduce extra impurity, influence product content, and added burden is caused to environment；In addition, petroleum ether is petrochemical industry by-product,
Its composition is complex, and has fractions to belong to high boiling substance, during last precipitation, although under higher vacuum,
There is still a need for reaching more than 60 DEG C of temperature, not only high energy consumption, clethodim are decomposed and become apparent.Because this reason, city at present
Clethodim product is typically 87% or so on field, and content is 90% or so.In spite of some documents and patent report to clethodim system
Standby technique is improved, and lifts its product yield and content, but still is laboratory stage, can not be converted into industrial chemical conversion
Fruit.
Patent 200910033391.6 provides a kind of improvement synthetic method of clethodim, and it is using petroleum ether as solvent, and third
Triketone and allyl oxygen amine are raw material, and low temperature synthesizes clethodim under conditions of ketone complex is as stabilizer, avoids clethodim
Because yield is low, content is low caused by pyrolytic the problem of.This method clethodim yield 97% or so, content 95% or so, than passing
System method has lifting, but reaction will add ketone complex, has the shortcomings that increase additional impurities, cost are high, and product extraction is still
The vacuum distillation of higher temperature is so used, still can cause the loss of clethodim.
Institutes Of Technology Of Nanjing Qian Yun master thesis have studied synthesis and its process optimization of clethodim, in the paper
The preparation method of clethodim is as follows：With 5- [2- (ethylmercapto group) propyl group] -2- propionos-hydroresorcinols and 3- chlorallyl hydroxyls
Amine is raw material, using n-hexane and water as solvent, the stirring reaction 24h at 60 DEG C.After reaction terminates, organic phase is collected in liquid separation, is added
Enter water sodium hydroxide adjustment pH to 13, remove organic phase, aqueous phase adds n-hexane, adjusts pH to 4, removes aqueous phase, organic phase water
Wash, dry, be concentrated under reduced pressure to obtain clethodim.This method is only laboratory stage, and reaction temperature is higher, and its last handling process is cumbersome,
Gained clethodim yield only 50%, if industrialized production yield is more difficult to ensure.
The content of the invention
In view of the deficienciess of the prior art, the invention provides a kind of industrialized process for preparing of clethodim, this method
Reaction condition is gentle, product purity and high income, is easy to industrial applications.
Technical solution of the present invention is as follows：
A kind of industrialized process for preparing of clethodim, this method include：Using dichloromethane as solvent, by 5- [2- (second sulphur
Base) propyl group] -2- propionos-hydroresorcinol and chloroallyl oxygen amine carries out reaction generation clethodim.
The present invention sets about being improved the preparation method of clethodim from solvent, and the petroleum ether that existing process is commonly used is changed into
Dichloromethane, research are found, after solvent is changed into dichloromethane, two raw materials can be reacted at a lower temperature, be improved
The stability of clethodim, at the same dichloromethane compared with petroleum ether can removed under reduced pressure at a lower temperature, both saved energy consumption,
Relatively low reaction temperature and precipitation temperature reduces the decomposition of clethodim again, improves the purity and yield of product.
Further, 5- [2- (ethylmercapto group) propyl group] -2- propiono -1 of the present invention, hydroresorcinol（Molecular weight 270g/
mol）With chloroallyl oxygen amine（Molecular weight 107.5g/mol）It can be reacted at a temperature of 20-25 DEG C, in this temperature
Under, the stability of product clethodim greatly improves.
Further, the present invention is improved for the desolventizing process of reaction solution, is replaced with by vacuum distillation precipitation
High vacuum falling film evaporation precipitation.High vacuum falling film evaporation precipitation can reduce precipitation temperature, be advantageous to improve product yield and
Content.
Further, temperature during high vacuum falling film evaporation precipitation of the present invention is 30-35 DEG C, high vacuum falling film evaporation precipitation
Vacuum（Absolute truth reciprocal of duty cycle）≤200pa.Energy consumption is greatly reduced compared with traditional more than 60 DEG C of precipitation temperature, is improved
The resolution ratio of clethodim.
Further, high vacuum falling film evaporation precipitation is realized by falling-film evaporation plant, such as falling film evaporator.
Further, 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, hydroresorcinol and chloroallyl oxygen amine rub
You are than being 1:1.05-1.3, preferably 1:1.05-1.1, more preferably 1:1.05.In existing process, typically using petroleum ether, just
The straight-chain hydrocarbons such as hexane are as solvent, 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, hydroresorcinol favorable solubility, but chlorine
It can not dissolve wherein, therefore be reacted to be heterogeneous, to reach high conversion, it is necessary to increase chloroallyl oxygen for pi-allyl oxygen amine
The inventory of amine（Ketoamine ratio is generally 1:1.3）, using dichloromethane as solvent after, 5- [2- (ethylmercapto group) propyl group] -2-
Wherein, therefore, it is possible to reduce chloroallyl oxygen amine propiono -1, hydroresorcinol and chloroallyl oxygen amine all can dissolve
(ketoamine ratio can be reduced to 1 to inventory:1.05) waste of raw material, is reduced.In addition, traditional handicraft amine is excessively big, after the completion of reaction,
The chloroallyl oxygen amine by excess is needed to be fallen with pickling, simultaneously because the absolute acid stability of clethodim product is very poor, it is necessary to make
It is in neutral state, therefore to increase the operations such as washing, regulation PH, and post processing is cumbersome, discharge of wastewater is big.And with dichloromethane
During as solvent, amine is excessively extremely limited, and the present invention carries out precipitation in the later stage using high vacuum falling-film distillation, and amine is in precipitation mistake
It can be steamed in journey with solvent, it is not necessary to extra process, simplify post-processing and wastewater discharge.
Further, the present invention is improved to the feed postition of raw material, so that at a lower reaction temperature also can be compared with
Fast completion reaction, improves reaction rate.Raw material feed postition is specific as follows：First chloroallyl oxygen amine is mixed with dichloromethane
Close, 5- [2- (ethylmercapto group) propyl group] -2- propiono -1 is then added dropwise into mixture again, hydroresorcinol is reacted.
Further, 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, the time for adding of hydroresorcinol is 1.5-2h,
After dripping, continue to react 1.5-2h.
Further, 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, hydroresorcinol and chloroallyl oxygen amine are close
Closed loop is reacted under border.
Further, solvent load can be adjusted according to being actually needed, the mass ratio of General reactions raw material and solvent
For 1:1-10.
The present invention has the advantage that：
1st, the present invention is replaced to solvent, can also entered in the case of being added without catalyst at a temperature of 20-25 DEG C
Row reaction, saves energy resource consumption, reduces the decomposition of clethodim, avoid the introducing of additional impurities, improve product yield
And content.
2nd, the present invention replaces vacuum distillation to remove solvent using high vacuum falling film evaporation, can be in 30-35 DEG C of low temperature
Lower carry out precipitation, product decomposition and energy resource consumption are reduced, while greatly improve product content and yield.
3rd, the present invention have adjusted the feed postition of raw material, and 5- [2- (ethylmercapto group) propyl group] -2- third is changed to by disposable mixing
Acyl group -1, the mode that hydroresorcinol is slowly dropped into, it raw material is more sufficiently mixed and is reacted, improve low
Reaction rate under temperature.
4th, the inventive method realizes the high content, in high yield of clethodim product in industrialization aspect, and clethodim content can
To reach 97% or more, yield has high economic benefit up to 98% or more.
Embodiment
The present invention is further detailed with specific embodiment below.Unless otherwise instructed, following reactions used into
The concentration divided is mass concentration.
Raw material chloroallyl oxygen amine used in the present invention can be obtained commercially, 5- [2- (ethylmercapto group) third
Base] -2- propiono -1, hydroresorcinol can be made according to disclosed method in the prior art, of the invention to be no longer described in detail.
Embodiment 1
In 3000L reactors, 800kg dichloromethane and 182 is added（Content 92%）Kg chloroallyl oxygen amine, mixing
It is 20-25 DEG C that temperature is controlled after uniformly, instills 420.4kg（Content 95%）5- [2- (ethylmercapto group) propyl group] -2- propionos -1,3-
Cyclohexanedione, time for adding 1.5-2h, continue to react 1.5-2h at 20-25 DEG C after dripping off, detection 5- [2- (ethylmercapto group) third
Base] -2- propiono -1, hydroresorcinol conversion ratio up to 99%, react by stopping.After reaction, reaction solution is subjected to high vacuum falling liquid film
Evaporation, remove dichloromethane, concrete operations：Falling-film evaporation plant high vacuum unit is opened, opens condenser salt solution cooling valve,
Reaction solution is squeezed into falling-film evaporation plant with transfering material pump, feed liquid forms film, dichloromethane and excess in falling-film evaporation plant
Chloroallyl oxygen amine with vacuum into gaseous state separate, be changed into liquid, recycled again by condenser.Clethodim product is then
Collection storage tank is flowed directly under gravity.Clethodim is collected into clethodim in storage tank and continues falling-film distillation operation, institute
Product sampling detection is obtained, until precipitation is complete.During precipitation, maintain temperature at 30-35 DEG C, the vacuum meter number of degrees maintain 200pa with
Under.
Clethodim 538kg is obtained after falling film evaporation, it is 97% to detect its content through HPLC, with 5- [2- (ethylmercapto group) propyl group] -2-
Propiono-hydroresorcinol rate of collecting is 98%.
Embodiment 2
In 3000L reactors, 1600kg dichloromethane and 364 is added（Content 92%）Kg chloroallyl oxygen amine, mixing
It is 20-25 DEG C that temperature is controlled after uniformly, then instills 841（94.9%）Kg5- [2- (ethylmercapto group) propyl group] -2- propionos -1,3-
Cyclohexanedione, time for adding 1.5-2h, continue to react 1.5-2h at 20-25 DEG C after dripping off, detection 5- [2- (ethylmercapto group) third
Base] -2- propiono -1, hydroresorcinol conversion ratio up to 99%, react by stopping.After reaction, reaction solution is subjected to high vacuum falling liquid film
Evaporation, dichloromethane and chloroallyl oxygen amine are removed, specific operation process is with example 1, and evaporating temperature is in 30-35 DEG C, vacuum
Degree is in below 200pa, and remaining liq is clethodim, common 1075.1kg.It is 97.1% to detect its content through HPLC, with 5- [2-
(ethylmercapto group) propyl group] -2- propionos-hydroresorcinol meter its yields is 98.1%.
Embodiment 3
In 3000L reactors, 1600kg dichloromethane and 364kg are added（92%）Chloroallyl oxygen amine, it is well mixed
It is 20-25 DEG C to control temperature afterwards, then instills 800kg（95%）5- [2- (ethylmercapto group) propyl group] -2- propiono -1,3- hexamethylenes two
Ketone, time for adding 1.5-2h, continue to react 1.5-2h at 20-25 DEG C after dripping off, detect chloroallyl oxygen amine conversion ratio
Up to 99%, stop reaction.After reaction, by reaction solution at 60 DEG C vacuum distillation, deviate from dichloromethane, obtain clethodim
997.3kg.It is 93.7% to detect its content through HPLC, with 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, hydroresorcinol meter
Its yield is 92.5%.
Embodiment 4
In 3000L reactors, 1600kg dichloromethane and 800kg are added（95%）5- [2- (ethylmercapto group) propyl group] -2- third
Acyl group -1, hydroresorcinol, it is 20-25 DEG C that temperature is controlled after well mixed, is then quickly added into 364kg chloroallyl oxygen amine
Reacted, after reacting 16h, detect 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, hydroresorcinol conversion ratio up to 99%,
Stop reaction.After reaction, reaction solution is subjected to high vacuum falling film evaporation, removes dichloromethane, specific operation process with example 1,
For evaporating temperature in 30-35 DEG C, vacuum in below 200pa, remaining liq is clethodim, common 1020.7kg.Detected through HPLC
Its content is 96.5%, and with 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, its yield of hydroresorcinol meter is 97.5%.
Embodiment 5
In 5000L reactors, 4000kg dichloromethane and 200kg are added（92%）Chloroallyl oxygen amine, it is well mixed
It is 20-25 DEG C to control temperature afterwards, instills 400kg5- [2- (ethylmercapto group) propyl group] -2- propiono -1, hydroresorcinol, during dropwise addition
Between be 1.5-2h, continue to react 1.5-2h at 20-25 DEG C after dripping off, detect 5- [2- (ethylmercapto group) propyl group] -2- propiono -1,
Hydroresorcinol conversion ratio up to 99%, stops reaction.After reaction, reaction solution is subjected to high vacuum falling film evaporation, removes dichloromethane
Alkane, specific operation process is with example 1, and for evaporating temperature in 30-35 DEG C, vacuum in below 200pa, remaining liq is alkene grass
Ketone, common 534.3kg.It is 96.8% to detect its content through HPLC, with 5- [2- (ethylmercapto group) propyl group] -2- propionos -1,3- hexamethylene two
Its yield of ketone meter is 97.2%.
Comparative example 1
In 3000L reactors, 800kg petroleum ethers and 400kg are added（95%）5- [2- (ethylmercapto group) propyl group] -2- propionyl
Base -1, hydroresorcinol, keeping temperature is 55-60 DEG C after stirring, and adds 200kg（92%）Chloroallyl oxygen amine, and
4h is reacted at a temperature of this, detects 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, hydroresorcinol conversion ratio up to 99%, stops
Reaction.After reaction terminates, reaction solution is deviate from into petroleum ether by the way of vacuum distillation, distillation vacuum is -0.095Mpa, temperature
Spend for 65-70 DEG C, obtain clethodim 496kg.It is 90.1% to detect its content through HPLC, with 5- [2- (ethylmercapto group) propyl group] -2- propionyl
Base-its yield of hydroresorcinol meter is 88.2%.
Comparative example 2
In 3000L reactors, 800kg petroleum ethers and 400kg are added（95%）5- [2- (ethylmercapto group) propyl group] -2- propionyl
Base -1, hydroresorcinol, keeping temperature is 20-25 DEG C after stirring, and adds 200kg（92%）Chloroallyl oxygen amine, and
Reacted at a temperature of this, after reacting 24h, detect 5- [2- (ethylmercapto group) propyl group] -2- propiono -1, hydroresorcinol conversion ratio is only up to
24.5%。
Claims (9)
1. a kind of industrialized process for preparing of clethodim, it is characterized in that：Using dichloromethane as solvent, by 5- [2- (ethylmercapto group) third
Base] -2- propiono -1, hydroresorcinol and chloroallyl oxygen amine carries out reaction generation clethodim, and reacted reaction solution leads to
The mode desolvation of too high vacuum falling film evaporation, obtains clethodim finished product, and during high vacuum falling film evaporation, temperature is 30-35 DEG C,
Absolute truth reciprocal of duty cycle≤200pa.
2. preparation method according to claim 1, it is characterized in that：Reaction temperature is 20-25 DEG C.
3. preparation method according to claim 1, it is characterized in that：5- [2- (ethylmercapto group) propyl group] -2- propiono -1,3- rings
The mol ratio of acetyl butyryl and chloroallyl amine is 1:1.05-1.3.
4. preparation method according to claim 3, it is characterized in that：5- [2- (ethylmercapto group) propyl group] -2- propiono -1,3- rings
The mol ratio of acetyl butyryl and chloroallyl amine is 1:1.05-1.1.
5. preparation method according to claim 1, it is characterized in that：High vacuum falling film evaporation is real by falling-film evaporation plant
It is existing.
6. preparation method according to claim 1, it is characterized in that：First chloroallyl oxygen amine is mixed with dichloromethane,
Then 5- [2- (ethylmercapto group) propyl group] -2- propionos-hydroresorcinol is added dropwise into mixture again to be reacted.
7. preparation method according to claim 6, it is characterized in that：5- [2- (ethylmercapto group) propyl group] -2- propiono -1,3- rings
The time for adding of acetyl butyryl is 1.5-2h, after dripping, continues to react 1.5-2h.
8. the preparation method according to claim 1 or 6, it is characterized in that：5- [2- (ethylmercapto group) propyl group] -2- propiono -1,
Hydroresorcinol and chloroallyl oxygen amine are reacted under closed environment.
9. preparation method according to claim 1, it is characterized in that：The mass ratio of reaction raw materials and solvent is 1:2-10.
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| CN113024425B (en) * | 2019-12-24 | 2022-05-17 | 沈阳科创化学品有限公司 | Preparation method of clethodim |
| 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 |
| WO2022034514A1 (en) * | 2020-08-11 | 2022-02-17 | Upl Limited | A process for preparation of clethodim |
| 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 |
| CN112961083B (en) * | 2021-02-08 | 2022-11-11 | 龙曦宁（上海）医药科技有限公司 | Synthesis method of clethodim impurities |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440566A (en) * | 1982-08-05 | 1984-04-03 | Chevron Research Company | Herbicidal substituted 2-(1-(oxyamino)-alkylidene)-cyclohexane-1,3-diones |
| CN86105662A (en) * | 1985-08-23 | 1987-04-08 | 切夫尔昂研究公司 | 2-[1-(3-chloroallyloxyimino) alkylidene]-5-alkyl alkylthio base-hexanaphthene-1,3 dione herbicides |
| US5228896A (en) * | 1990-05-09 | 1993-07-20 | Basf Aktiengesellschaft | Cyclohexenone oxime ethers, their preparation, intermediates for their preparation and their use as 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 |
| CN101575307A (en) * | 2009-06-11 | 2009-11-11 | 江苏长青农化股份有限公司 | Synthetic method of clethodim |
| CN105418470A (en) * | 2015-11-17 | 2016-03-23 | 江苏长青农化股份有限公司 | Synthetic method of clethodim |
-
2016
- 2016-07-08 CN CN201610533417.3A patent/CN106187841B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440566A (en) * | 1982-08-05 | 1984-04-03 | Chevron Research Company | Herbicidal substituted 2-(1-(oxyamino)-alkylidene)-cyclohexane-1,3-diones |
| CN86105662A (en) * | 1985-08-23 | 1987-04-08 | 切夫尔昂研究公司 | 2-[1-(3-chloroallyloxyimino) alkylidene]-5-alkyl alkylthio base-hexanaphthene-1,3 dione herbicides |
| US5228896A (en) * | 1990-05-09 | 1993-07-20 | Basf Aktiengesellschaft | Cyclohexenone oxime ethers, their preparation, intermediates for their preparation and their use as 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 |
| CN101575307A (en) * | 2009-06-11 | 2009-11-11 | 江苏长青农化股份有限公司 | Synthetic method of clethodim |
| CN105418470A (en) * | 2015-11-17 | 2016-03-23 | 江苏长青农化股份有限公司 | Synthetic method of clethodim |
Non-Patent Citations (4)
| Title |
|---|
| 农药烯草酮的合成工艺改进;吴迎晓;《浙江大学硕士学位论文》;20050331;第1-51页 * |
| 烯草酮合成工艺热危险性及动力学;程春生 等;《农药》;20140210;第53卷(第2期);第99-101页 * |
| 除草剂烯草酮的合成研究;王芳;《吉林大学硕士学位论文》;20061031;第1-82页 * |
| 除草剂烯草酮的合成研究进展;郭林华 等;《现代农药》;20060210;第5卷(第1期);第5-8页 * |
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