CN106187841A - 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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- CN106187841A CN106187841A CN201610533417.3A CN201610533417A CN106187841A CN 106187841 A CN106187841 A CN 106187841A CN 201610533417 A CN201610533417 A CN 201610533417A CN 106187841 A CN106187841 A CN 106187841A
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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 the industrialized process for preparing of a kind of clethodim, with dichloromethane as solvent, by 5 [2 (ethylmercapto group) propyl group] 2 propionos 1,3 cyclohexanediones and chloroallyl oxygen amine carry out reaction and generate clethodim.Solvent is replaced by the present invention, also can react at a temperature of 20 25 DEG C, save energy resource consumption, decrease the decomposition of clethodim in the case of being added without catalyst, it is to avoid the introducing of additional impurities, improves product yield and content.
Description
Technical field
The present invention relates to the preparation method of a kind of clethodim, be specifically related to the clethodim of a kind of mild condition, low cost
Industrialized process for preparing, belongs to clethodim preparing technical field.
Background technology
Clethodim, English name clethodim, happy logical, the seroxat of another name receipts, chemical name: (±)-2-［ (E)-3-chlorine alkene
Propoxyl group imino group ］ propyl group-5-[2-ethylsuleenyl propyl]-3-hydroxyl-2-cyclohexene-1-ketone, belong to cyclonene
Class herbicide.Clethodim is the cyclohexenone analog herbicide developed by Chevron chemical company of the U.S. nineteen eighty-two, and this medicine is interior
Inhale conduction type height selective post-emergence herbicide, to broad leaf crop safety, can be used for the multiple dicotyledonous works such as Semen sojae atricolor, Cotton Gossypii, Brassica campestris L
Thing field, the annual and perennial grassy weed such as effective Control Wild oat, Brachiaria Griseb, black Herba bromi japonici, Herba Digitariae, Herba Setariae Viridis.
The trade name that Chevron chemical company of the U.S. uses is received happy logical medicine and is used for many years in China, and this product removes
Grass effect is always fine, receives trust and the welcome of vast farmers, is the important active substance of a class in pesticide field, tool
There are high-efficiency broad spectrum biological activity and the plurality of advantages such as environmentally friendly, it has also become the new lover in market, market prospect is the most wide.
At present, the preparation method of industrial conventional clethodim is: (1), with crotonic aldehyde, ethyl mercaptan as raw material, triethylamine does
Catalyst synthesis 3-ethylmercapto group butyraldehyde；(2) with ethyl acetoacetate, liquid caustic soda as raw material, water is solvent synthesis of acetyl acetic acid sodium salt；
(3) with 3-ethylmercapto group butyraldehyde, acetoacetic acid sodium salt as raw material, toluene makees solvent, piperidines makees catalyst, acetic acid regulates pH in reaction
Value synthesis 6-ethylmercapto group-3-alkene-2-heptanone；(4) 6-ethylmercapto group-3-alkene-2-heptanone-toluene solution and diethyl malonate are in first
Carry out cyclization reaction in the presence of sodium alkoxide, add propionyl chloride after dealcoholysis and be acylated, PDM(i.e. DMAP) catalytically rearranging, then through liquid caustic soda water
Solution, salt acid decarboxylation, petroleum ether extraction generate 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 after high vacuum distillation, obtain fine work 5-
[2-(ethylmercapto group) propyl group]-2-propiono-hydroresorcinol；(5) fine work 5-[2-(ethylmercapto group) propyl group]-2-propiono-1,
Hydroresorcinol and chloroallyl oxygen amine generate clethodim with petroleum ether for solvent reaction.Each step reaction equation is as follows:
In traditional method, with 5-[2-(ethylmercapto group) propyl group]-2-propiono-1, hydroresorcinol is former with chloroallyl oxygen amine
Concretely comprising the following steps of clethodim prepared by material: 5-[2-(ethylmercapto group) propyl group]-2-propiono-hydroresorcinol is added petroleum ether
In, keep temperature to be 55-60 DEG C after stirring, be subsequently adding chloroallyl oxygen amine, maintain the temperature at 55-60 DEG C and react,
Detection 5-[2-(ethylmercapto group) propyl group]-2-propiono-1, when hydroresorcinol content is less than 0.5%, reaction terminates, and then uses sour water
Washing, the vacuum distillation when 60-80 DEG C, deviate from aqueous solvent, obtain clethodim.Clethodim technical pesticide activity is high, easily degrades, especially
It is temperature sensitive, just has the most significantly decompose when temperature is higher than 20 DEG C, therefore, under existing reaction temperature, react into
Just there is portioned product to start to decompose during row, if reducing reaction temperature, then need the addition of catalyst, but add catalyst meeting
Introduce extra impurity, affect product content, environment is caused added burden；Additionally, petroleum ether is petrochemical industry by-product, it becomes
Divide complex, and have fractions to belong to high boiling substance, during last precipitation, although under higher vacuum, still
Needing to reach the temperature of more than 60 DEG C, not only energy consumption is high, and clethodim decomposition becomes apparent from.Since this reason, in the market
Clethodim product is typically about 87%, and content is about 90%.Despite some documents and patent report, clethodim is prepared work
Skill improves so that it is product yield and content promote, but still are laboratory stage, it is impossible to be converted into industrialization effort.
Patent 200910033391.6 provides the improvement synthetic method of a kind of clethodim, and it is with petroleum ether as solvent, and third
Triketone and allyl oxygen amine is raw material, low temperature synthesis clethodim under conditions of ketone coordination compound is as stabilizer, it is to avoid clethodim
The problem that the yield caused because of pyrolytic is low, content is low.The method clethodim yield about 97%, content about 95%, than biography
System method has lifting, but reacts ketone coordination compound to be added, and has increase additional impurities, high in cost of production shortcoming, and product extracts still
So use the decompression distillation of higher temperature, still can cause the loss of clethodim.
The master thesis of Institutes Of Technology Of Nanjing Qian Yun have studied synthesis and the process optimization thereof of clethodim, in this paper
The preparation method of clethodim is as follows: with 5-[2-(ethylmercapto group) propyl group]-2-propiono-hydroresorcinol and 3-chlorallyl hydroxyl
Amine is raw material, with normal hexane and water as solvent, and stirring reaction 24h at 60 DEG C.After reaction terminates, separatory collects organic facies, adds
Entering water sodium hydroxide and adjust pH to 13, remove organic facies, aqueous phase adds normal hexane, adjusts pH to 4, removes aqueous phase, organic phase washed with water
Washing, be dried, concentrating under reduced pressure obtains clethodim.The method is only laboratory stage, and reaction temperature is higher, and its last handling process is loaded down with trivial details,
Gained clethodim yield only 50%, if industrialized production yield is more difficult to ensure.
Summary of the invention
The deficiency existed for prior art, the invention provides the industrialized process for preparing of a kind of clethodim, the method
Reaction condition is gentle, and product purity and yield are high, it is simple to industrial applications.
Technical solution of the present invention is as follows:
The industrialized process for preparing of a kind of clethodim, the method includes: with dichloromethane as solvent, by 5-[2-(ethylmercapto group) third
Base]-2-propiono-hydroresorcinol and chloroallyl oxygen amine carries out reaction and generates clethodim.
The present invention sets about improving the preparation method of clethodim from solvent, is changed into by the petroleum ether that existing technique is conventional
Dichloromethane, research finds, after solvent becomes dichloromethane, two raw materials can react at a lower temperature, improves
The stability of clethodim, simultaneously 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 reduce again the decomposition of clethodim, improve purity and the yield of product.
Further, 5-of the present invention [2-(ethylmercapto group) propyl group]-2-propiono-1, hydroresorcinol (molecular weight 270g/
Mol) can react at a temperature of 20-25 DEG C, in this temperature with chloroallyl oxygen amine (molecular weight 107.5g/mol)
Under, the stability of product clethodim is greatly improved.
Further, the present invention is improved for the desolventizing operation of reactant liquor, decompression distillation precipitation replace with
Fine vacuum falling film evaporation precipitation.Fine vacuum falling film evaporation precipitation can reduce precipitation temperature, be conducive to improve product yield and
Content.
Further, temperature during fine vacuum falling film evaporation precipitation of the present invention is 30-35 DEG C, fine vacuum falling film evaporation precipitation
Vacuum (Absolute truth reciprocal of duty cycle)≤200pa.Greatly reduce energy consumption compared with the precipitation temperature of traditional more than 60 DEG C, improve
The resolution ratio of clethodim.
Further, fine 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, rubbing of hydroresorcinol and chloroallyl oxygen amine
That ratio is 1:1.05-1.3, preferably 1:1.05-1.1, more preferably 1:1.05.In existing technique, generally use 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
Can not dissolve wherein for pi-allyl oxygen amine, therefore reaction is for heterogeneous, for reaching high conversion, it is necessary to increase chloroallyl oxygen
The inventory (ketoamine ratio is generally 1:1.3) of amine, after using dichloromethane as solvent, 5-[2-(ethylmercapto group) propyl group]-2-
Propiono-1, hydroresorcinol and chloroallyl oxygen amine all solubilized wherein, therefore, it can reduce chloroallyl oxygen amine
Inventory (ketoamine ratio can reduce to 1:1.05), decreases the waste of raw material.Additionally, traditional handicraft amine excess is big, after having reacted,
The chloroallyl oxygen amine pickling by excess is needed to fall, 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 operation such as washing, regulation PH, and post processing is loaded down with trivial details, discharge of wastewater is big.And with dichloromethane
During as solvent, amine excess is extremely limited, and the present invention uses fine vacuum falling-film distillation to carry out precipitation in the later stage, and amine is in precipitation mistake
Journey can steam with solvent, it is not necessary to extra process, simplify later stage process and wastewater discharge.
Further, the feed postition of raw material is improved by the present invention, so that the most also can be relatively
Fast completes reaction, improves reaction rate.Raw material feed postition is specific as follows: first mixed with dichloromethane by chloroallyl oxygen amine
Closing, drip 5-[2-(ethylmercapto group) propyl group]-2-propiono-1 the most again in mixture, hydroresorcinol reacts.
Further, 5-[2-(ethylmercapto group) propyl group]-2-propiono-1, the time for adding of hydroresorcinol is 1.5-2h,
After dripping, continue reaction 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 actual needs, General reactions raw material and the mass ratio of solvent
For 1:1-10.
Present invention have the advantage that
1, solvent is replaced by the present invention, also can carry out anti-in the case of being added without catalyst at a temperature of 20-25 DEG C
Should, save energy resource consumption, decrease the decomposition of clethodim, it is to avoid the introducing of additional impurities, improve product yield and contain
Amount.
2, the present invention use fine vacuum falling film evaporation replace decompression distillation to remove solvent, can be at the low temperature of 30-35 DEG C
Under carry out precipitation, reduce Disassembling Products and energy resource consumption, greatly improve product content and yield simultaneously.
3, the present invention have adjusted the feed postition of raw material, disposable mixing change 5-[2-(ethylmercapto group) propyl group]-2-third into
Acyl group-1, the mode that hydroresorcinol is slowly dropped into, raw material so can be made the most sufficiently to mix and react, improve low
Reaction rate under Wen.
4, the inventive method achieves the high-load of clethodim product, high yield in industrialization aspect, and clethodim content can
With reach 97% or more than, yield up to 98% or more than, there is high economic benefit.
Detailed description of the invention
With specific embodiment, the present invention is further detailed below.If no special instructions, react into used by following
The concentration divided is mass concentration.
Raw material chloroallyl oxygen amine used by the present invention can commercially obtain, 5-[2-(ethylmercapto group) third
Base]-2-propiono-1, hydroresorcinol can prepare according to the method disclosed in prior art, and the present invention no longer describes in detail.
Embodiment 1
In 3000L reactor, add 800kg dichloromethane and 182(content 92%) kg chloroallyl oxygen amine, mix homogeneously
Rear control temperature is 20-25 DEG C, instills 420.4kg(content 95%) 5-[2-(ethylmercapto group) propyl group]-2-propiono-1,3-hexamethylene
Diketone, time for adding is 1.5-2h, continue after dripping off at 20-25 DEG C react 1.5-2h, detection 5-[2-(ethylmercapto group) propyl group]-
2-propiono-1, hydroresorcinol conversion ratio has reached 99%, stopped reaction.After reaction, reactant liquor is carried out fine vacuum falling liquid film steaming
Send out, remove dichloromethane, concrete operations: open falling-film evaporation plant fine vacuum unit, open condenser saline cooling valve, will
Reactant liquor transfering material pump squeezes into falling-film evaporation plant, and feed liquid forms thin film, dichloromethane and excess in falling-film evaporation plant
Chloroallyl oxygen amine becomes gaseous state to separate with vacuum, again becomes liquid, recycled through condenser.Clethodim product then exists
Collection storage tank is flowed directly under action of gravity.Clethodim is collected clethodim in storage tank and proceeds falling-film distillation operation, gained
Product sampling detection, until precipitation is complete.During precipitation, maintaining temperature at 30-35 DEG C, the vacuum meter number of degrees maintain below 200pa.
Obtaining clethodim 538kg after falling film evaporation, detecting its content through HPLC is 97%, with 5-[2-(ethylmercapto group) propyl group]-2-
Propiono-hydroresorcinol rate of collecting is 98%.
Embodiment 2
In 3000L reactor, add 1600kg dichloromethane and 364(content 92%) kg chloroallyl oxygen amine, mix homogeneously
Rear control temperature is 20-25 DEG C, then instills 841(94.9%) kg5-[2-(ethylmercapto group) propyl group]-2-propiono-1,3-hexamethylene
Diketone, time for adding is 1.5-2h, continue after dripping off at 20-25 DEG C react 1.5-2h, detection 5-[2-(ethylmercapto group) propyl group]-
2-propiono-1, hydroresorcinol conversion ratio has reached 99%, stopped reaction.After reaction, reactant liquor is carried out fine vacuum falling liquid film steaming
Sending out, remove dichloromethane and chloroallyl oxygen amine, specific operation process is with example 1, and evaporating temperature is 30-35 DEG C, vacuum
At below 200pa, remaining liq is clethodim, altogether 1075.1kg.Detecting its content through HPLC is 97.1%, with 5-[2-(second
Sulfenyl) propyl group]-2-propiono-its yield of hydroresorcinol meter is 98.1%.
Embodiment 3
In 3000L reactor, add 1600kg dichloromethane and 364kg(92%) chloroallyl oxygen amine, control after mix homogeneously
Temperature processed is 20-25 DEG C, then instills 800kg(95%) 5-[2-(ethylmercapto group) propyl group]-2-propiono-1, hydroresorcinol, drips
Adding the time is 1.5-2h, continues to react 1.5-2h after dripping off at 20-25 DEG C, and detection chloroallyl oxygen amine conversion ratio reaches
99%, stopped reaction.After reaction, by reactant liquor vacuum distillation when 60 DEG C, deviate from dichloromethane, obtain clethodim 997.3kg.Warp
It is 93.7% that HPLC detects its content, and with 5-[2-(ethylmercapto group) propyl group]-2-propiono-1, its yield of hydroresorcinol meter is
92.5%。
Embodiment 4
In 3000L reactor, add 1600kg dichloromethane and 800kg(95%) 5-[2-(ethylmercapto group) propyl group]-2-propionyl
Base-1, hydroresorcinol, control temperature after mix homogeneously and be 20-25 DEG C, be then quickly added into 364kg chloroallyl oxygen amine and enter
Row reaction, after reaction 16h, detects 5-[2-(ethylmercapto group) propyl group]-2-propiono-1, and hydroresorcinol conversion ratio has reached 99%, stopped
Only reaction.After reaction, reactant liquor carrying out fine vacuum falling film evaporation, remove dichloromethane, specific operation process, with example 1, is steamed
Send out temperature 30-35 DEG C, vacuum be clethodim at below 200pa, remaining liq, altogether 1020.7kg.It is detected through HPLC
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 reactor, add 4000kg dichloromethane and 200kg(92%) chloroallyl oxygen amine, control after mix homogeneously
Temperature processed is 20-25 DEG C, instills 400kg5-[2-(ethylmercapto group) propyl group]-2-propiono-1, and hydroresorcinol, time for adding is
1.5-2h, continues to react 1.5-2h at 20-25 DEG C, detects 5-[2-(ethylmercapto group) propyl group]-2-propiono-1,3-ring after dripping off
Acetyl butyryl conversion ratio has reached 99%, stopped reaction.After reaction, reactant liquor is carried out fine vacuum falling film evaporation, removes dichloromethane,
Specific operation process with example 1, evaporating temperature 30-35 DEG C, vacuum be clethodim at below 200pa, remaining liq, altogether
534.3kg.Detecting its content through HPLC is 96.8%, with 5-[2-(ethylmercapto group) propyl group]-2-propiono-1, hydroresorcinol meter
Its yield is 97.2%.
Comparative example 1
In 3000L reactor, add 800kg petroleum ether and 400kg(95%) 5-[2-(ethylmercapto group) propyl group]-2-propiono-1,
Hydroresorcinol, keeps temperature to be 55-60 DEG C, adds 200kg(92% after stirring) chloroallyl oxygen amine, and temperature at this
Reacting 4h under degree, detect 5-[2-(ethylmercapto group) propyl group]-2-propiono-1, hydroresorcinol conversion ratio has reached 99%, stops anti-
Should.After reaction terminates, reactant liquor using the mode of vacuum distillation deviate from petroleum ether, distillation vacuum is-0.095Mpa, temperature
For 65-70 DEG C, obtain clethodim 496kg.Detecting its content through HPLC is 90.1%, with 5-[2-(ethylmercapto group) propyl group]-2-propionyl
Base-its yield of hydroresorcinol meter is 88.2%.
Comparative example 2
In 3000L reactor, add 800kg petroleum ether and 400kg(95%) 5-[2-(ethylmercapto group) propyl group]-2-propiono-1,
Hydroresorcinol, keeps temperature to be 20-25 DEG C, adds 200kg(92% after stirring) chloroallyl oxygen amine, and temperature at this
The lower reaction of degree, after reaction 24h, detects 5-[2-(ethylmercapto group) propyl group]-2-propiono-1, and hydroresorcinol conversion ratio is only up to
24.5%。
Claims (10)
1. an industrialized process for preparing for clethodim, is characterized in that: with dichloromethane as solvent, by 5-[2-(ethylmercapto group) third
Base]-2-propiono-3-hydroxyl-2-cyclohexene-1-ketone and chloroallyl amine carries out reaction and generates clethodim.
Preparation method the most according to claim 1, is characterized in that: reaction temperature is 20-25 DEG C.
Preparation method the most according to claim 1, is characterized in that: 5-[2-(ethylmercapto group) propyl group]-2-propiono-3-hydroxyl
The mol ratio of base-2-cyclohexene-1-ketone and chloroallyl amine is 1:1.05-1.3, preferably 1:1.05-1.1.
4. according to the preparation method according to any one of claim 1-3, it is characterized in that: reacted reactant liquor passes through fine vacuum
The mode desolvation of falling film evaporation, obtains clethodim finished product.
Preparation method the most according to claim 4, is characterized in that: during fine vacuum falling film evaporation, and temperature is 30-35 DEG C, absolutely
To vacuum≤200pa.
6. according to the preparation method described in claim 4 or 5, it is characterized in that: falling-film evaporation plant is passed through in fine vacuum falling film evaporation
Realize.
Preparation method the most according to claim 1, is characterized in that: first mixed with dichloromethane by chloroallyl amine, so
After again in mixture drip 5-[2-(ethylmercapto group) propyl group]-2-propiono-3-hydroxyl-2-cyclohexene-1-ketone react.
Preparation method the most according to claim 7, is characterized in that: 5-[2-(ethylmercapto group) propyl group]-2-propiono-3-hydroxyl
The time for adding of base-2-cyclohexene-1-ketone is 1.5-2h, after dripping, continues reaction 1.5-2h.
9. according to the preparation method described in claim 1 or 7, it is characterized in that: 5-[2-(ethylmercapto group) propyl group]-2-propiono-3-
Hydroxyl-2-cyclohexene-1-ketone and chloroallyl amine react under closed environment.
Preparation method the most according to claim 1, is characterized in that: reaction raw materials is 1:2-10 with the mass ratio of solvent.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111892520A (en) * | 2020-08-28 | 2020-11-06 | 山东潍坊润丰化工股份有限公司 | Environment-friendly synthesis 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 |
| CN112500322A (en) * | 2020-12-01 | 2021-03-16 | 安道麦安邦(江苏)有限公司 | Production method of clethodim preparation |
| CN112961083A (en) * | 2021-02-08 | 2021-06-15 | 龙曦宁（上海）医药科技有限公司 | Synthesis method of clethodim impurities |
| CN113024425A (en) * | 2019-12-24 | 2021-06-25 | 沈阳科创化学品有限公司 | Preparation method of clethodim |
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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 |
| CN111892520A (en) * | 2020-08-28 | 2020-11-06 | 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 |
| CN112961083A (en) * | 2021-02-08 | 2021-06-15 | 龙曦宁（上海）医药科技有限公司 | Synthesis method of clethodim impurities |
| 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 |
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