CN106946785A - A kind of synthesis technique of pyraclostrobin intermediate pyrazole alcohol - Google Patents
A kind of synthesis technique of pyraclostrobin intermediate pyrazole alcohol Download PDFInfo
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- CN106946785A CN106946785A CN201710250608.3A CN201710250608A CN106946785A CN 106946785 A CN106946785 A CN 106946785A CN 201710250608 A CN201710250608 A CN 201710250608A CN 106946785 A CN106946785 A CN 106946785A
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- kettle
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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
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
- C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
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Abstract
The invention discloses a kind of synthesis technique of pyraclostrobin intermediate pyrazole alcohol, the process specifically includes following steps：The ketone of 1 (4 chlorphenyl) pyrazolidine 3 is put into reactor, add solvent DMF and be passed through oxygen 56 hours, it was incubated for 1 small time, oxidation reaction is transferred to precipitation kettle after terminating, DMF is reclaimed in evaporation, precipitation adds water after terminating washs centrifugation, solid phase obtains the pyrazoles alcohol of light yellow solid 1 (4 chlorphenyl) 3, the present invention being capable of effective recycling design after initial reaction terminates by pyraclostrobin intermediate pyrazole alcohol, synthesis cost is saved, improve economic benefit, optimize the synthesis technique design of pyraclostrobin intermediate pyrazole alcohol, meet the requirement of the synthesis technique design of pyraclostrobin intermediate pyrazole alcohol.
Description
Technical field
The present invention relates to pesticide synthesis technical field, and in particular to a kind of synthesis work of pyraclostrobin intermediate pyrazole alcohol
Skill.
Background technology
Methoxy acrylic disinfectant is a class low toxicity, efficient, wide spectrum, interior absorption bactericide, is world pesticide circle
The novel agrochemical bactericide of great development potentiality and the market vitality；Pyraclostrobin is the best methoxy acrylic acid of current activity
Esters bactericide, it is the earliest developmental research of BASF Aktiengesellschaft, and is released in 2002 in European market；Pyrazoles ether bacterium
Ester has efficient, low toxicity, the extensive shortcoming of environmentally friendly, applicable crops；A few years since being listed from pyraclostrobin,
The market of the kind is risen violently rapidly, and sales volume rises rapidly, has been classified as the second in all microbial inoculum kind markets, has been only second to phonetic bacterium
Ester.
Pyraclostrobin is the methoxy acrylic bactericide for having pyrrazole structure concurrently, and 1993 public by German BASF
Department finds, registers and lists within 2001, has been used at present in 100 various crops；2009, its sales volume reached that 7.35 hundred million is beautiful
Member, is only second to Fluoxastrobin, as world's second largest bactericide；Pyraclostrobin wide spectrum, efficient, toxicity are low, to non-target organism
Safety, it is friendly to user and environment safety, it is that good market prospect in strobilurin series bactericidal agents, patent will mistakes
The staple product of phase.
The conventional method of mix reagent crystallization is, when solvent degree is fine in certain solvent for organic matter, first to use being somebody's turn to do for minimum
Solvent carries out heating for dissolving, reheats the slightly worse another solvent of solubility, reduces the solubility of the organic matter, then cooling analysis
Go out crystal；Either product is dissolved with the solvent of minimal amount of favorable solubility at reflux, then from condenser pipe
The relatively low solvent of dissolubility is added, to solution Hun Chi, then the drop that flows back is clear, and cooling is separated out；But this method can crystallize product
Not exclusively, solvent recovery is not thorough, so as to influence the yield of product, increases post processing cost.
The synthetic route of original pyraclostrobin intermediate pyrazole alcohol there is a series of problems, it is necessary to explore one can
Capable handling process route, for solving problems with：
1. agitator is not provided with inside oxidizing reactor or mixing parametric sets unreasonable so that pyraclostrobin
The combined coefficient of intermediate pyrazole alcohol is low, low yield, is unfavorable for large-scale production；
2. the organic liquid after precipitation is without washing, cause to contain DMF impurity in final product, influence product
Purity and actually used value, are unfavorable for economy, are also unsatisfactory for the actual requirement of environmental protection safety；
Reacted, introduced new 3. the not purified direct sets of the DMF reclaimed by precipitation are used in oxidizing reactor
Impurity, the liquid phase obtained after centrifugal treating is used for set and reproduction is carried out in oxidizing reactor, wastes production cost, no
Beneficial to economy.
The content of the invention
To solve the above problems, the present invention proposes a kind of synthesis technique of pyraclostrobin intermediate pyrazole alcohol.
To realize the object of the invention, the technical scheme of use is：A kind of synthesis work of pyraclostrobin intermediate pyrazole alcohol
Skill, the process specifically includes following steps：
(1) is aoxidized：1- (4- chlorphenyls) pyrazolidine -3- ketone is put into oxidizing reactor, from the top of oxidizing reactor
Side adds solvent DMF, is continually fed into oxygen for a period of time from oxidizing reactor top side end, is stirred using agitator, in oxygen
Change in reactor and be persistently incubated 1 hour, oxidation reaction is transferred to precipitation kettle after terminating；
(2) precipitations：Organic solution in oxidizing reactor containing DMF is transferred in precipitation kettle, made in precipitation kettle
It is stirred with agitator, heating evaporation DMF, the DMF that evaporation forms steam is transferred to solvent recovery tower and reclaimed, and enters back into
Stored in solvent groove；
(3) is washed：The organic solution for deviating from DMF by precipitation kettle is transferred in washing kettle, in the stirring action of agitator
Under be passed through deionized water and washed, static layering after washing, water layer and organic layer are produced from washing tower bottom respectively, after washing
Water layer feeding sewage treatment plant processing；
(4) is centrifuged：The organic layer produced from washing kettle is transferred to inside centrifuge, is set after relevant parameter, opens centrifugation
Machine is centrifuged, and solid phase obtains light yellow solid 1- (4- chlorphenyls) -3- pyrazoles alcohol, and liquid phase carries out recycling reproduction.
It is preferred that, the logical oxygen time is 5~6 hours inside the oxidizing reactor, and the stir speed (S.S.) of agitator is 500-
1500 turns/min, the outer wrap of agitator has noise-reduction device.
It is preferred that, evaporation DMF mode is agitator stirring speed in a kind of flash distillation mode, precipitation kettle inside the precipitation kettle
Rate is set to 1500~3000 turns/min, and the outer wrap of agitator has noise-reduction device.
It is preferred that, the DMF steam by flashing generation in precipitation kettle carries out cooling condensation inside solvent recovery tower, cold
Solidifying temperature is 5 DEG C~20 DEG C, and cooling medium is water, and condensed liquid D MF is transferred to solvent groove.
It is preferred that, the washing temperature set inside the washing kettle is 50 DEG C~70 DEG C, and the stir speed (S.S.) of agitator is 500
~1000 turns/min, the outer wrap of agitator has noise-reduction device.
It is preferred that, spiral heating coiled pipe, described spiral heating coiled pipe are provided with the oxidizing reactor and precipitation kettle
Design height is the 1/2~2/3 of oxidizing reactor and precipitation kettle height, and the caliber of spiral heating coiled pipe is 2~5cm, spiral coil
Number is 15~40 circles.
It is preferred that, the Design of Centrifuge is a kind of disk centrifugal separator, wherein, the centrifugal barrel a diameter of 60 of disk centrifugal separator
~80cm, disk centrifugal separator centrifugal rotational speed turns/min to be set to 4000-10000.
Compared with prior art, the beneficial effects of the invention are as follows：A kind of pyraclostrobin intermediate involved in the present invention
The synthesis technique of pyrazoles alcohol, the process specifically includes following steps：By 1- (4- chlorphenyls) pyrazolidine -3- ketone input
In reactor, add solvent DMF and be passed through oxygen 5-6 hours, be incubated for 1 small time, oxidation reaction is transferred to precipitation kettle after terminating, steam
Beam back receipts DMF, precipitation adds water washing centrifugation after terminating, and solid phase obtains light yellow solid 1- (4- chlorphenyls) -3- pyrazoles alcohol, with
Lower advantage：
1. the synthesis technique of pyraclostrobin intermediate pyrazole alcohol of the present invention, enters after oxidation reaction to solvent
Effective recovery is gone, the solvent after recovery can be put into production, save synthesis cost, improve economic benefit again；
2. the synthesis technique of pyraclostrobin intermediate pyrazole alcohol of the present invention, solution is remained in by washing recovery
In DMF, improve the purity of product, it is to avoid occur impurity in product, the water layer after washing can apply mechanically with to DMF steam
Condensation, lifts economy；
3. the synthesis technique of pyraclostrobin intermediate pyrazole alcohol of the present invention, the organic liquid layer after centrifugation is returned
Receive to reproduction in oxidizing reactor, embody economy and practicality, optimize the conjunction of pyraclostrobin intermediate pyrazole alcohol
Into technological design, the requirement of the synthesis technique design of pyraclostrobin intermediate pyrazole alcohol is met.
Brief description of the drawings
Fig. 1 is the synthesis process flow diagram of pyraclostrobin intermediate pyrazole alcohol of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Embodiment 1
Refer to shown in Fig. 1, the technical solution adopted by the present invention is：A kind of synthesis of pyraclostrobin intermediate pyrazole alcohol
Technique, the process specifically includes following steps：
(1) is aoxidized：1- (4- chlorphenyls) pyrazolidine -3- ketone is put into oxidizing reactor, from the top of oxidizing reactor
Side adds solvent DMF, is continually fed into oxygen for a period of time from oxidizing reactor top side end, is stirred using agitator, in oxygen
Change in reactor and be persistently incubated 1 hour, oxidation reaction is transferred to precipitation kettle after terminating；
(2) precipitations：Organic solution in oxidizing reactor containing DMF is transferred in precipitation kettle, made in precipitation kettle
It is stirred with agitator, heating evaporation DMF, the DMF that evaporation forms steam is transferred to solvent recovery tower and reclaimed, and enters back into
Stored in solvent groove；
(3) is washed：The organic solution for deviating from DMF by precipitation kettle is transferred in washing kettle, in the stirring action of agitator
Under be passed through deionized water and washed, static layering after washing, water layer and organic layer are produced from washing tower bottom respectively, after washing
Water layer feeding sewage treatment plant processing；
(4) is centrifuged：The organic layer produced from washing kettle is transferred to inside centrifuge, is set after relevant parameter, opens centrifugation
Machine is centrifuged, and solid phase obtains light yellow solid 1- (4- chlorphenyls) -3- pyrazoles alcohol, and liquid phase carries out recycling reproduction.
Operation principle：When using, 1- (4- chlorphenyls) pyrazolidine -3- ketone of purification process is put into oxidizing reactor
It is interior, solvent DMF is added in the top side of oxidizing reactor, oxygen is passed through from the top side of oxidizing reactor, sets and stir
Mix after device mixing parametric, persistently stirred using agitator 5~6 hours, use the spiral heating snake being arranged in oxidizing reactor
Pipe carries out insulation 1 hour, and the liquid in oxidizing reactor is transferred in precipitation kettle, entered in precipitation kettle by reaction to be oxidized after terminating
Row flash vaporization DMF, the DMF steam of generation carries out condensation inside solvent recovery tower and is recycled to solvent groove, organic liquid warp
Cross after precipitation kettle precipitation terminates and be transferred in washing kettle, static layering after the washing that added water in washing kettle, water layer is transferred to sewage
Treatment plant is handled or is applied in solvent recovery tower as low-temperature receiver, and organic layer goes in centrifuge and centrifuged, and is centrifuged
Solid phase obtains light yellow solid 1- (4- chlorphenyls) -3- pyrazoles alcohol afterwards, oxidation is applied to after the residue that liquid phase is obtained is purified anti-
Answer and reproduction is carried out in kettle.
Further, the logical oxygen time is 5~6 hours inside the oxidizing reactor, and the stir speed (S.S.) of agitator is 500-
1500 turns/min, the outer wrap of agitator has noise-reduction device.
Further, evaporation DMF mode is that agitator is stirred in a kind of flash distillation mode, precipitation kettle inside the precipitation kettle
Speed is set to 1500~3000 turns/min, and the outer wrap of agitator has noise-reduction device.
Further, the DMF steam by flashing generation in precipitation kettle carries out cooling condensation inside solvent recovery tower,
Condensation temperature is 5 DEG C~20 DEG C, and cooling medium is water, and condensed liquid D MF is transferred to solvent groove.
Further, the washing temperature set inside the washing kettle is 50 DEG C~70 DEG C, and the stir speed (S.S.) of agitator is
500~1000 turns/min, the outer wrap of agitator has noise-reduction device.
Further, spiral heating coiled pipe, described spiral heating snake are provided with the oxidizing reactor and precipitation kettle
Pipe design height is the 1/2~2/3 of oxidizing reactor and precipitation kettle height, and the caliber of spiral heating coiled pipe is 2~5cm, spiral
The number of turns is 15~40 circles.
Further, the Design of Centrifuge is a kind of disk centrifugal separator, wherein, the centrifugal barrel of disk centrifugal separator is a diameter of
60~80cm, disk centrifugal separator centrifugal rotational speed turns/min to be set to 4000-10000.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understand and these embodiments can be carried out without departing from the principles and spirit of the present invention a variety of changes, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (7)
1. a kind of synthesis technique of pyraclostrobin intermediate pyrazole alcohol, it is characterised in that：The process is specifically included
Following steps：
(1) is aoxidized：1- (4- chlorphenyls) pyrazolidine -3- ketone is put into oxidizing reactor, from the top side of oxidizing reactor
Solvent DMF is added, oxygen is continually fed into for a period of time from oxidizing reactor top side end, is stirred using agitator, it is anti-in oxidation
Answer and 1 hour is persistently incubated in kettle, oxidation reaction is transferred to precipitation kettle after terminating；
(2) precipitations：Organic solution in oxidizing reactor containing DMF is transferred in precipitation kettle, using stirring in precipitation kettle
Mix device to be stirred, heating evaporation DMF, the DMF that evaporation forms steam is transferred to solvent recovery tower and reclaimed, and enters back into molten
Stored in agent groove；
(3) is washed：The organic solution for deviating from DMF by precipitation kettle is transferred in washing kettle, is led under the stirring action of agitator
Enter deionized water to be washed, static layering after washing, water layer and organic layer are produced from washing tower bottom respectively, the water after washing
The processing of layer feeding sewage treatment plant；
(4) is centrifuged：The organic layer produced from washing kettle is transferred to inside centrifuge, is set after relevant parameter, is opened centrifuge and is entered
Row centrifugation, solid phase obtains light yellow solid 1- (4- chlorphenyls) -3- pyrazoles alcohol, and liquid phase carries out recycling reproduction.
2. the synthesis technique of pyraclostrobin intermediate pyrazole alcohol according to claim 1, it is characterised in that：The oxidation
The logical oxygen time is 5~6 hours inside reactor, and the stir speed (S.S.) of agitator turns/min, the outside bag of agitator for 500-1500
It is wrapped with noise-reduction device.
3. the synthesis technique of pyraclostrobin intermediate pyrazole alcohol according to claim 1, it is characterised in that：The precipitation
Inside kettle evaporation DMF mode be in a kind of flash distillation mode, precipitation kettle agitator stir speed (S.S.) be set to 1500~3000 turns/
Min, the outer wrap of agitator has noise-reduction device.
4. the synthesis technique of pyraclostrobin intermediate pyrazole alcohol according to claim 1, it is characterised in that：It is described by taking off
The DMF steam that flash distillation is produced in molten kettle carries out cooling condensation inside solvent recovery tower, and condensation temperature is 5 DEG C~20 DEG C, condensation
Medium is water, and condensed liquid D MF is transferred to solvent groove.
5. the synthesis technique of pyraclostrobin intermediate pyrazole alcohol according to claim 1, it is characterised in that：The washing
The washing temperature set inside kettle is 50 DEG C~70 DEG C, and the stir speed (S.S.) of agitator is outside 500~1000 turns/min, agitator
Portion is enclosed with noise-reduction device.
6. the synthesis technique of pyraclostrobin intermediate pyrazole alcohol according to claim 1, it is characterised in that：The oxidation
Spiral heating coiled pipe is provided with reactor and precipitation kettle, described spiral heating coiled pipe design height is oxidizing reactor and de-
The 1/2~2/3 of molten kettle height, the caliber of spiral heating coiled pipe is 2~5cm, and spiral number of turns are 15~40 circles.
7. the synthesis technique of pyraclostrobin intermediate pyrazole alcohol according to claim 1, it is characterised in that：The centrifugation
Machine is designed as a kind of disk centrifugal separator, wherein, a diameter of 60~80cm of centrifugal barrel of disk centrifugal separator, disk centrifugal separator centrifugation turns
Speed turns/min to be set to 4000-10000.
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| CN201710250608.3A CN106946785A (en) | 2017-04-17 | 2017-04-17 | A kind of synthesis technique of pyraclostrobin intermediate pyrazole alcohol |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592117A (en) * | 2015-01-13 | 2015-05-06 | 安徽国星生物化学有限公司 | Synthesis method of pyraclostrobin |
| CN105111148A (en) * | 2015-08-10 | 2015-12-02 | 安徽国星生物化学有限公司 | 2-[(N-para-chlorophenyl)-3-pyrazole oxymethyl]nitrobenzene and preparation method therefor and application thereof |
| WO2016113741A1 (en) * | 2015-01-14 | 2016-07-21 | Adama Makhteshim Ltd. | Process for preparing 1-(4-chlorophenyl)-3-[(2-nitrophenyl)methoxy]-1h-pyrazole |
| CN105968048A (en) * | 2016-06-07 | 2016-09-28 | 四川福思达生物技术开发有限责任公司 | Method for synthesizing pyraclostrobin intermediate 1-(4-chlorophenyl)-3-hydroxy-1-h-pyrazole |
-
2017
- 2017-04-17 CN CN201710250608.3A patent/CN106946785A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592117A (en) * | 2015-01-13 | 2015-05-06 | 安徽国星生物化学有限公司 | Synthesis method of pyraclostrobin |
| WO2016113741A1 (en) * | 2015-01-14 | 2016-07-21 | Adama Makhteshim Ltd. | Process for preparing 1-(4-chlorophenyl)-3-[(2-nitrophenyl)methoxy]-1h-pyrazole |
| CN105111148A (en) * | 2015-08-10 | 2015-12-02 | 安徽国星生物化学有限公司 | 2-[(N-para-chlorophenyl)-3-pyrazole oxymethyl]nitrobenzene and preparation method therefor and application thereof |
| CN105968048A (en) * | 2016-06-07 | 2016-09-28 | 四川福思达生物技术开发有限责任公司 | Method for synthesizing pyraclostrobin intermediate 1-(4-chlorophenyl)-3-hydroxy-1-h-pyrazole |
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