CN106866537A - A kind of production technology of ethiprole - Google Patents
A kind of production technology of ethiprole Download PDFInfo
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- CN106866537A CN106866537A CN201710255483.3A CN201710255483A CN106866537A CN 106866537 A CN106866537 A CN 106866537A CN 201710255483 A CN201710255483 A CN 201710255483A CN 106866537 A CN106866537 A CN 106866537A
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- ethiprole
- acetic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of production technology of ethiprole, comprises the following steps：1) stills for air blowing, plus acetic acid are taken, the amino-pyrazol of 14 second sulfydryl of (2,6 dichloro-4,4 trifluoromethyl) 3 cyano group of phenyl 5 is put into, material all dissolves in being heated to kettle；2) lower the temperature, hydrogen peroxide is added dropwise, obtain oxidation liquid；3) distillation still is gone to, sodium sulfite is put into, water and acetic acid is first evaporated off, turn material to washing kettle；4) lower the temperature, add water, stratification, organic layer adds water washing, blowing suction filtration, filter cake goes to centrifuge, and centrifugal solids turn refining kettle；5) ethanol is put into, backflow is warming up to, is cooled；6) turn material to crystallization kettle, be cooled to crystallization, be centrifuged, centrifugal solids drying obtains finished product ethiprole.The synthesis route sets reasonable, and production process green non-pollution thing discharge, the recyclable recycling of solvent for use, gained ethiprole purity is high, and yield is good, good disinsection effect, can effectively reduce production cost, energy-saving, good in economic efficiency.
Description
Technical field
The invention belongs to insecticide synthesis material production technical field, specifically, being related to a kind of production technology of ethiprole.
Background technology
Ethiprole molecular formula C13H9Cl2F3N4OS, molecular weight 397.20, as insecticide, chemical name 1- (2,6- bis-
Chloro- 4- trifluoromethyls) -3- cyano group -4- ethylsulfinyl -5- amino-pyrazols, ethiprole (Ethiprole) is by Luo Na
Planck finds, the Insecticidal and acaricidal agent of Beyer Co., Ltd's exploitation, belongs to the second generation and acts under the low consumption of insecticide of GABA to many
Plant chewing type and sucking pest effectively, can be used for Seed Treatment and foliar spray, the lasting period is up to 21-28d.(it is mainly used in
Some aleyrodids are also shown activity (particularly right by preventing and treating thrips, stinkbug, curculionid, beet gelechiid, aphid, plant hopper and locust etc.
The rice grub green rice bug of extremely difficult preventing and treating has very strong activity）.
Ethiprole belongs to benzene pyrazoles broad spectrum pesticide, and its mechanism of action is to disturb chloride channel by GABA,
So as to destroy central nervous system normal activity, make insect lethal.With organic phosphates, pyrethroid, carbamates
Do not exist cross resistance problem etc. main insecticide.Its mode of action is contact, is laid out absorbability.To various chewing types and
Sucking pest has prevention effect.Through toxicity biologic test and field control effectiveness test, as a result show ethiprole pair
Rice hoppers have preferably activity and prevention effect.
For the synthesis technique of ethiprole, the current country is primarily present following patent document：
China Patent Publication No.：CN104370818A, discloses the technique that a kind of oxidizing process prepares high-purity ethiprole, will be appropriate
Raw material 5- Amino 3 cyanos -1-（2,6- dichlor-4-trifluoromethyl phenyl）- 4- ethylsulfinyl-1 base pyrazoles（I）In organic solvent
In, there is oxidation reaction in the case where aliphatic acid, hydrogen peroxide are participated in, after the completion of oxidation reaction, add reducing agent control system simultaneously
Temperature, then adjusts system acid-base value with NaOH solution, then crystallisation by cooling suction filtration obtains crude product ethiprole after temperature rising reflux, slightly
Product ethiprole（Ⅱ）It is purified to can obtain certified products；Wherein, organic solvent is from chloroform, dichloromethane, dichloroethanes
It is at least one.Simple production process of the present invention, efficiency high, accessory substance are few, are obtained on product yield and product purity
Larger breakthrough, and material toxicity is relatively low, and environmental pollution is smaller, and production controllability is good.
The content of the invention
To solve above-mentioned problem, it is an object of the invention to provide a kind of production technology of ethiprole, the work
Skill is simple to operate, and synthetic route sets reasonable, the discharge of production process green non-pollution thing, the recyclable recycling of solvent for use,
Gained ethiprole purity is high, and yield is good, can be used with various insecticide compositions, and good disinsection effect can effectively reduce production cost,
It is energy-saving, it is good in economic efficiency.
To reach above-mentioned purpose, the technical scheme is that：
A kind of production technology of ethiprole, comprises the following steps：
1) stills for air blowing, plus acetic acid are taken, moisture≤0.2wt% in acetic acid puts into 1- (2,6- dichlor-4-trifluoromethyl) phenyl -3-
Cyano group -4- second sulfydryl -5- amino-pyrazols, stirring, are warming up to 30 ~ 50 DEG C, and material all dissolves in insulation reaction to kettle；
2) be cooled to 20~25 DEG C, hydrogen peroxide be added dropwise, during dropwise addition controlling reaction temperature at 20~25 DEG C, be warming up to 35~
40 DEG C, insulation reaction 6~10 hours samples middle control analysis, and pyrazoles peak area percent≤3% is reaction end, obtains oxidation reaction
Liquid；
3) by step 2) gained oxidation liquid goes to distillation still, to sodium sulfite is put into kettle, controls 75 ~ 80 DEG C of temperature, stir
Mix 20 ~ 40 minutes, water and acetic acid is successively evaporated off, it is steamed, turn material to washing kettle；
4) 15 ~ 20 DEG C are cooled to, are added water, stratification after stirring washing, a point water layer goes wastewater treatment, and organic layer continues to add water
Washing, blowing suction filtration, filtrate goes wastewater treatment, and filter cake goes to centrifuge, and centrifugate goes wastewater treatment, centrifugal solids to turn essence
Kettle processed；
5) to ethanol is put into refining kettle, backflow is warming up to, is flowed back 20 ~ 40 minutes, cooled to 25 ~ 35 DEG C；
6) turn material to crystallization kettle, be cooled to crystallization, be centrifuged, centrifuge mother liquor goes ethanol to reclaim kettle, and centrifugal solids drying obtains finished product
Ethiprole.
Further, step 1) described in acetic acid and 1- (2,6- dichlor-4-trifluoromethyl) phenyl -3- cyano group -4- second sulfydryl -
The addition mass ratio of 5- amino-pyrazols is 3 ~ 4：1, kg/kg.
Preferably, the step 1) in insulation reaction when a length of 40 ~ 80 minutes.
Preferably, the step 2) in, hydrogen peroxide addition is 1 with the mass ratio of the acetic acid：9 ~ 10, the hydrogen peroxide
It is 27.5% hydrogen peroxide.
Preferably, step 3) described in the mass ratio of sodium sulfite addition and the acetic acid be 1：15 ~ 20, kg/kg.
Preferably, step 3) in water and acetic acid is evaporated off successively under the conditions of≤80 DEG C, -0.09Mpa, the water being evaporated off removes waste water
Process tank, acetic acid receiving tank is entered after the acetic acid that is evaporated off is condensed.
Preferably, step 4) in amount of water in acetic acid addition mass ratio be 1：5 ~ 6, kg/kg；Organic layer washes water consumption
It is 1 with acetic acid addition mass ratio：2 ~ 3, kg/kg；Organic layer washing times are 1 ~ 3 time.
Preferably, step 5) described in amount of alcohol added and acetic acid addition mass ratio be 1：1 ~ 1.5, kg/kg.
Preferably, step 6) in, 0 DEG C of crystallization is cooled to, centrifugal solids are dried under the conditions of 55 ~ 65 DEG C, -0.08Mpa.
Preferably, the step 6) in, ethanol is reclaimed and comprised the following steps：The ethanol that heats up reclaims kettle, 70 ~ 90
DEG C, steam ethanol under condition of normal pressure, it is condensed after enter ethanol receiving slit, deliver to step 5) recycled production, steamed, the residual work of kettle
It is solidification disposal of waste.
The beneficial effects of the present invention are：
The technological operation is simple, and synthetic route sets reasonable, and production process green non-pollution thing discharge, solvent for use is recyclable
Recycling, gained ethiprole purity is high, and content can reach 99.7%, and color is pure white, and acetone insoluble matter is less than 0.1%, its
Its all kinds of impurity is below 0.1%.Yield is good, with 1- (2,6- dichlor-4-trifluoromethyl) phenyl -3- cyano group -4- second sulfydryls -5-
Amino-pyrazol rate of collecting can reach 95%, can be used with various insecticide compositions, and good disinsection effect can effectively reduce production cost,
It is energy-saving, it is good in economic efficiency.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
A kind of production technology of ethiprole of the present invention, comprises the following steps：
1) from acetic acid head tank（From storage tank zone acetic acid basin）To being put into acetic acid 1700kg in 3000L stills for air blowing, sampling is sent point
Analysis center analysis moisture content, moisture content≤0.2% side can downward operation, 1- (2,6- bis- chloro- 4- fluoroforms are put into kettle from charge door
Base) phenyl -3- cyano group -4- second sulfydryl -5- amino-pyrazol 450kg, stirring is opened, it is warming up to 40 DEG C, insulation reaction 1 hour, to kettle
Middle material all after dissolving, opens chilled brine cooling；
2) 27.5% hydrogen peroxide 167kg is added dropwise into kettle from hydrogen peroxide head tank at 20~25 DEG C, reaction temperature is controlled during dropwise addition
At 20~25 DEG C, completion of dropwise addition continues insulation reaction about 6~10 hours, sampling analysis, when pyrazoles peak≤3% to degree in 35~40 DEG C
It is reaction end, obtains oxidation liquid；
3) oxidation liquid is gone into 3000L acetic acid distillation stills, sodium sulfite 100Kg, control temperature is put into kettle from charge door
Degree stirs half an hour below 80 DEG C, and water is first then evaporated off under the conditions of≤80 DEG C, -0.09Mpa（Go wastewater treatment）, steam afterwards
Go out acetic acid, it is condensed after enter acetic acid receiving tank, it is steamed, turn material to 3000L washing kettles；
4) 3000L washing kettles cool to less than 20 DEG C, plus 300kg water, and stratification after stirring washing, a point water layer is gone at waste water
Reason, organic layer continues the 800Kg washings 2 times that add water.
5) stirring is cooled to less than 20 DEG C, is then discharged to nutsch filter suction filtration, and filtrate goes wastewater treatment, and filter cake goes to centrifugation
Machine is centrifuged, and centrifugate enters mother liquor tank and goes wastewater treatment, centrifugal solids to turn refining kettle；
6) ethanol 1500kg is put into refining kettle from ethanol head tank, is warming up to 80 DEG C of backflow half an hour, then cooled
To 30 DEG C；
7) turn material to crystallization kettle, continue to be cooled to 0 DEG C of crystallization, then feeding, to centrifuge, centrifuge mother liquor enters mother liquor tank（Go second
Alcohol is reclaimed）, centrifugal solids deliver to double-cone dryer, are dried under the conditions of 60 DEG C, -0.08Mpa（Ethanol is reclaimed to cover for producing）,
Product ethiprole is obtained, gained ethiprole purity is high, and content can reach 99.7%, and color is pure white, and acetone insoluble matter is less than
0.1%, other all kinds of impurity are below 0.1%.Yield is good, with 1- (2,6- dichlor-4-trifluoromethyl) phenyl -3- cyano group -4- second
Sulfydryl -5- amino-pyrazol rate of collecting can reach 95%, can be used with various insecticide compositions, and good disinsection effect can effectively reduce life
Cost is produced, it is energy-saving, it is good in economic efficiency.
Ethanol is reclaimed：
Intensification ethanol reclaims kettle, steams ethanol under 80 DEG C, condition of normal pressure, it is condensed after enter ethanol receiving slit, steamed, the residual work of kettle
It is solidification disposal of waste.
It should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted.Although with reference to compared with
Good embodiment has been described in detail to the present invention, it will be understood by those within the art that, can be to the technology of invention
Scheme is modified or equivalent, and without deviating from the scope of technical solution of the present invention, it all should cover in power of the invention
In sharp claimed range.
Claims (10)
1. a kind of production technology of ethiprole, it is characterised in that comprise the following steps：
1) stills for air blowing, plus acetic acid are taken, moisture≤0.2wt% in acetic acid puts into 1- (2,6- dichlor-4-trifluoromethyl) phenyl -3- cyanogen
Base -4- second sulfydryl -5- amino-pyrazols, stirring, are warming up to 30 ~ 50 DEG C, and material all dissolves in insulation reaction to kettle；
2) 20~25 DEG C are cooled to, hydrogen peroxide is added dropwise, holding is added dropwise 50Kg per hour, and controlling reaction temperature is 20 during dropwise addition
~25 DEG C, 35~40 DEG C are warming up to, insulation reaction 6~10 hours samples middle control analysis, and pyrazoles peak area percent≤3% is anti-
Terminal is answered, oxidation liquid is obtained；
3) by step 2) gained oxidation liquid goes to distillation still, to sodium sulfite is put into kettle, controls 75 ~ 80 DEG C of temperature, stir
Mix 20 ~ 40 minutes, water and acetic acid is successively evaporated off, it is steamed, turn material to washing kettle；
4) 15 ~ 20 DEG C are cooled to, are added water, stratification after stirring washing, a point water layer goes wastewater treatment, and organic layer continues the water that adds water
Wash, blowing suction filtration, filtrate goes wastewater treatment, filter cake goes to centrifuge, and centrifugate goes wastewater treatment, centrifugal solids to turn refined
Kettle；
5 in refining kettle to ethanol is put into, and is warming up to backflow, is flowed back 20 ~ 40 minutes, is cooled to 25 ~ 35 DEG C；
6) turn material to crystallization kettle, be cooled to crystallization, be centrifuged, centrifuge mother liquor goes ethanol to reclaim kettle, and centrifugal solids drying obtains finished product second
Worm nitrile.
2. a kind of production technology of ethiprole according to claim 1, it is characterised in that step 1) described in acetic acid and 1-
The addition mass ratio of (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -4- second sulfydryl -5- amino-pyrazols is 3 ~ 4：1, kg/
kg。
3. a kind of production technology of ethiprole according to claim 1, it is characterised in that the step 1) in insulation reaction
Shi Changwei 40 ~ 80 minutes.
4. a kind of production technology of ethiprole according to claim 1, it is characterised in that the step 2) in, hydrogen peroxide
Addition is 1 with the mass ratio of the acetic acid：9 ~ 10, the hydrogen peroxide is 27.5% hydrogen peroxide.
5. a kind of production technology of ethiprole according to claim 1, it is characterised in that step 3) described in sodium sulfite
Addition is 1 with the mass ratio of the acetic acid：15 ~ 20, kg/kg.
6. a kind of production technology of ethiprole according to claim 1, it is characterised in that step 3) in≤80 DEG C ,-
Water and acetic acid is evaporated off under the conditions of 0.09Mpa successively, the water being evaporated off removes waste water treatment tank, entering acetic acid after the acetic acid being evaporated off is condensed connects
Closed cans.
7. a kind of production technology of ethiprole according to claim 1, it is characterised in that step 4) in amount of water in acetic acid
Addition mass ratio is 1：5 ~ 6, kg/kg；It is 1 that organic layer washes water consumption with acetic acid addition mass ratio：2 ~ 3, kg/kg；Have
Machine layer washing times are 1 ~ 3 time.
8. a kind of production technology of ethiprole according to claim 1, it is characterised in that step 5) described in ethanol add
Amount is 1 with acetic acid addition mass ratio：1 ~ 1.5, kg/kg.
9. a kind of production technology of ethiprole according to claim 1, it is characterised in that step 6) in, it is cooled to 0 DEG C of knot
Crystalline substance, centrifugal solids are dried under the conditions of 55 ~ 65 DEG C, -0.08Mpa.
10. a kind of production technology of ethiprole according to claim 1, it is characterised in that the step 6) in, ethanol is returned
Receipts comprise the following steps：The ethanol of heating up reclaims kettle, steams ethanol under 70 ~ 90 DEG C, condition of normal pressure, it is condensed after enter ethanol
Receiving slit, delivers to step 5) recycled production, steamed, kettle is residual as solidification disposal of waste.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204322A (en) * | 1995-12-20 | 1999-01-06 | 罗纳-普朗克农业化学公司 | Novel 5-amino-3-cyano-4-ethylsulfinyl-1-phenyl-pyrazole compounds and their use as pesticides |
| CN1242002A (en) * | 1996-12-24 | 2000-01-19 | 罗纳-普朗克农业化学公司 | Pesticidal 1-arylpyrazoles |
| CN101228134A (en) * | 2005-06-15 | 2008-07-23 | 辉瑞有限公司 | Substituted arylpyrazoles as antiparasitic agent |
| CN104370818A (en) * | 2014-11-10 | 2015-02-25 | 浙江海正化工股份有限公司 | Process for preparing high-purity ethiprole through oxidation method |
-
2017
- 2017-04-19 CN CN201710255483.3A patent/CN106866537A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204322A (en) * | 1995-12-20 | 1999-01-06 | 罗纳-普朗克农业化学公司 | Novel 5-amino-3-cyano-4-ethylsulfinyl-1-phenyl-pyrazole compounds and their use as pesticides |
| CN1242002A (en) * | 1996-12-24 | 2000-01-19 | 罗纳-普朗克农业化学公司 | Pesticidal 1-arylpyrazoles |
| CN101228134A (en) * | 2005-06-15 | 2008-07-23 | 辉瑞有限公司 | Substituted arylpyrazoles as antiparasitic agent |
| CN104370818A (en) * | 2014-11-10 | 2015-02-25 | 浙江海正化工股份有限公司 | Process for preparing high-purity ethiprole through oxidation method |
Non-Patent Citations (1)
| Title |
|---|
| WEN, LI-RONG ET AL.,: "Reaction of Enaminones with Aminopyrazoles: Synthesis, Structures and Bioactivities of 7-Aryl-3-cyano-2-substituted Pyrazolo[1,5-a]pyrimidines", 《CHINESE JOURNAL OF CHEMISTRY》 * |
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Application publication date: 20170620 |