CN106632046A - Synthesis method of pyraclostrobin - Google Patents
Synthesis method of pyraclostrobin Download PDFInfo
- Publication number
- CN106632046A CN106632046A CN201611140585.2A CN201611140585A CN106632046A CN 106632046 A CN106632046 A CN 106632046A CN 201611140585 A CN201611140585 A CN 201611140585A CN 106632046 A CN106632046 A CN 106632046A
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- CN
- China
- Prior art keywords
- pyraclostrobin
- synthetic method
- hydroxy
- aniline
- pyrazoles
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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
Abstract
The invention relates to a synthesis method of pyraclostrobin. The method comprises the following steps: 1) adding N-hydroxy-N-2-[N-(4-chlorophenyl) pyrazolyl-3-oxymethyl]aniline and triethylamine into a reaction solution, stirring, and heating; 2) dropwisely adding iodomethane to carry out methylation reaction, and keeping the temperature; 3) neutralizing by washing with water, and standing to stratify; and 4) recovering methylbenzene, adding isopropanol, crystallizing, and filtering to obtain the pyraclostrobin pure product. The synthesis method reduces the damage to the human body and environment, and requires low acid-binding agent consumption. The method enhances the yield of the product, and further lowers the generation of byproducts. The method is simple to operate, and has the advantages of high raw material conversion rate and high yield and content (respectively 98% or above).
Description
Technical field
The present invention relates to pesticide synthesis technical field, more particularly to a kind of synthetic method of pyraclostrobin.
Background technology
Pyraclostrobin (Pyraclostrobin) also known as pyraclostrobin, are that BASF Aktiengesellschaft found in 1993
A kind of methoxy methyl acrylate class wide-spectrum bactericide for having pyrrazole structure concurrently.Its structural formula is：
Chemical name is：N- methoxyl group-N-2- [(N- rubigan) -3- pyrazoles epoxide methyl] carbanilate.
The medical instrument has the bactericidal activity of wide spectrum, and extensively, chief crop market is soybean, cereal, corn, grape and fruits and vegetables to applicable crops.
Herms etc. had found the ability that pyraclostrobin can improve tobacco mosaic disease resisting poison and tobacco Pseudomonas alba in 2002.It was both
The plant caused by the almost all kinds of fungal pathogens such as ascus guiding principle, Basidiomycetes, Fungi Imperfecti and Oomycete can be prevented and treated
Disease, is again a kind of hormone-type bactericide.It has toxicity low, safe, safe to user and environment to non-target organism
Friendly the characteristics of.
In prior art, the Chinese patent literature of Publication No. CN102399190A discloses a kind of economical synthesizing pyrazole
Kresoxim-methyl and its method, and specifically disclose following technical characteristic：By N- hydroxy-n -2- [(N- rubigan) -3- pyrazoles epoxides
Methyl] carbanilate and acid binding agent be added in polar solvent or non-polar solven, and sulfuric acid two is added after being well mixed
Methyl esters, at 20-30 DEG C, after the completion of Jing HPLC monitoring reactions, adds water, is neutralized to pH=7, and desolvation uses recrystallization solvent
Submergence, after being recrystallized, removes recrystallization solution, obtains pyraclostrobin；Described N- hydroxy-n -2- [(N- rubigan) -
3- pyrazoles epoxide methyl] carbanilate, acid binding agent, dimethyl suflfate mol ratio be 1: 1-1.8: 1-1.8.Although adopting
The yield of product, but the methylating reagent for adopting can be improved for dimethyl suflfate, dimethyl suflfate category with the technical scheme
In highly toxic substance (similar to mustard gas), and corrosivity is strong, it is careless slightly during use i.e. can be to human body skin and internal organ
System produces harm, and causes high risks to environment.Simultaneously as there is sulfuric acid to generate in building-up process, still need using big
The inorganic strong alkali of amount, so as to generate substantial amounts of inorganic salts, not only severe corrosion equipment, also add the difficulty of Separation ＆ Purification.
The content of the invention
In order to solve the deficiency of prior art presence, it is an object of the invention to provide a kind of synthesis side of pyraclostrobin
Method, using triethylamine as the acid binding agent in reaction, using iodomethane as methylating reagent, the process for making synthesis is more pacified
Entirely, to the friendly safety of user and environment, the yield of pyraclostrobin is improve, reduce further the generation of accessory substance.
For achieving the above object, the synthetic method of the pyraclostrobin that the present invention is provided, comprises the following steps：
1) N- hydroxy-n -2- [N- (4- chlorphenyls) pyrazoles -3- oxygen methyl] aniline, triethylamine are added into reaction dissolvent
In, heat after stirring；
2) iodomethane is added dropwise carries out methylation reaction and then is incubated；
3) washing neutralization, stratification are carried out；
4) toluene is reclaimed, adds isopropanol crystallization to filter, obtain pyraclostrobin sterling.
Further, step 1) reaction solution is toluene or dichloroethanes；The mixing time is 15 minutes；Heating
To 30 DEG C.
Further, step 2) methylation reaction, equation is as follows：
Further, the iodomethane and the N- hydroxy-ns -2- [N- (4- chlorphenyls) pyrazoles -3- oxygen methyl] aniline
Mol ratio is 1.01:1；The triethylamine rubs with the N- hydroxy-ns -2- [N- (4- chlorphenyls) pyrazoles -3- oxygen methyl] aniline
You are than being 1.01:1.
Further, step 4) temperature retention time be 3 hours.
Further, the step 4) it is further comprising the steps：
Toluene is reclaimed in vacuum distillation；
Cooling the temperature to 5 DEG C carries out crystallization filtration.
Compared with prior art, the present invention has advantages below：
1st, the present invention uses iodomethane as methylating reagent；Methylation reaction is carried out, relative to adopting in prior art
Dimethyl suflfate reduces the injury to human body and environment as methylating reagent, reduces the consumption of acid binding agent；
2nd, the present invention uses triethylamine as acid binding agent/catalyst, further increases the yield of pyraclostrobin, enters one
Step reduces the generation of accessory substance；
3rd, feed stock conversion of the invention is high, simple to operate, and yield and content all reach more than 98%.
Other features and advantages of the present invention will be illustrated in the following description, also, the partly change from specification
Obtain it is clear that or being understood by implementing the present invention.
Specific embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
The synthetic method of the pyraclostrobin of the present invention, with N- hydroxy-n -2- [N- (4- chlorphenyls) pyrazoles -3- oxygen methyl]
Aniline is raw material, under triethylamine catalysis, iodomethane is added dropwise at a certain temperature, carries out methylation reaction, through post processing behaviour
Pyraclostrobin sterling is obtained.
The present invention pyraclostrobin synthetic method be using triethylamine as reaction in acid binding agent, using iodomethane as
Methylating reagent carries out methylation reaction, and reaction dissolvent is using toluene or dichloroethanes, and methylation reaction formula is as follows：
In the present invention, mol ratio of the iodomethane with respect to N- hydroxy-n -2- [N- (4- chlorphenyls) pyrazoles -3- oxygen methyl] aniline
For 1.01:1；Triethylamine catalyst is with respect to the mol ratio of N- hydroxy-n -2- [N- (4- chlorphenyls) pyrazoles -3- oxygen methyl] aniline
1.01：1.
In the examples below that, " % " representation quality percentage.
Embodiment 1：
In the there-necked flask of 1L add N- hydroxy-n -2- [N- (4- chlorphenyls) pyrazoles -3- oxygen methyl] aniline (37.7g,
99%), (10.3g, 99%) with toluene (300mL), is stirred at room temperature 15 minutes triethylamine, is then heated to 30 DEG C of dropwise addition iodomethane
(14.5g, 99%), is incubated 3 hours, then washing neutralization, stratification, and toluene, remaining oily are reclaimed in then vacuum distillation
Thing adds recrystallization solvent isopropanol to be down to 5 DEG C of crystallizations and filters to obtain faint yellow solid 38.7g, and HPLC determines (external standard) content
98.2%, yield：98.2%.Mp (fusing point)：64-65℃.
Embodiment 2：
In the there-necked flask of 1L add N- hydroxy-n -2- [N- (4- chlorphenyls) pyrazoles -3- oxygen methyl] aniline (37.7g,
99%), (10.3g, 99%) with dichloroethanes (300mL), is stirred at room temperature 15 minutes triethylamine, is then heated to 30 DEG C of dropwise addition iodine
(14.5g, 99%), is incubated 3 hours, then washing neutralization to methane, stratification, and toluene is reclaimed in then vacuum distillation, remaining
Grease adds recrystallization solvent isopropanol to be down to 5 DEG C of crystallizations and filters to obtain faint yellow solid 38.9g, and HPLC determines (external standard) content
98.5%, yield：98.9%.Mp (fusing point)：64-65℃.
One of ordinary skill in the art will appreciate that：The foregoing is only the preferred embodiments of the present invention, and without
In the present invention is limited, although being described in detail to the present invention with reference to the foregoing embodiments, for those skilled in the art
For, it still can modify to the technical scheme that foregoing embodiments are recorded, or which part technical characteristic is entered
Row equivalent.All any modification, equivalent substitution and improvements within the spirit and principles in the present invention, made etc., all should include
Within protection scope of the present invention.
Claims (6)
1. a kind of synthetic method of pyraclostrobin, it is characterised in that the method comprising the steps of：
1）N- hydroxy-n -2- [N- (4- chlorphenyls) pyrazoles -3- oxygen methyl] aniline, triethylamine are added in reaction solution, are stirred
Heat after mixing；
2）Iodomethane is added dropwise to carry out methylation reaction and then is incubated；
3）Carry out washing neutralization, stratification；
4）Toluene is reclaimed, adds isopropanol crystallization to filter, obtain pyraclostrobin sterling.
2. the synthetic method of pyraclostrobin according to claim 1, it is characterised in that step 1）The reaction solution is first
Benzene or dichloroethanes；The mixing time is 15 minutes；It is heated to 30 DEG C.
3. the synthetic method of pyraclostrobin according to claim 1, it is characterised in that step 2）The methylation reaction,
Equation is as follows：
。
4. according to any one of claim 1-3 pyraclostrobin synthetic method, it is characterised in that the iodomethane and institute
The mol ratio for stating N- hydroxy-n -2- [N- (4- chlorphenyls) pyrazoles -3- oxygen methyl] aniline is 1.01:1；The triethylamine with it is described
The mol ratio of N- hydroxy-n -2- [N- (4- chlorphenyls) pyrazoles -3- oxygen methyl] aniline is 1.01:1.
5. the synthetic method of pyraclostrobin according to claim 1, it is characterised in that step 4）The temperature retention time is 3
Hour.
6. the synthetic method of pyraclostrobin according to claim 1, it is characterised in that the step 4）Further include with
Lower step：
Toluene is reclaimed in vacuum distillation；
Cooling the temperature to 5 DEG C carries out crystallization filtration.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107021927A (en) * | 2017-03-28 | 2017-08-08 | 天津大学 | A kind of pyraclostrobin crystal formation and preparation method thereof |
| CN108117521A (en) * | 2018-03-05 | 2018-06-05 | 安徽国星生物化学有限公司 | A kind of reversed recrystallization method of pyraclostrobin |
| CN110105287A (en) * | 2019-05-23 | 2019-08-09 | 江苏禾本生化有限公司 | A kind of synthesis technology of pyraclostrobin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154692A (en) * | 1994-07-06 | 1997-07-16 | 巴斯福股份公司 | 2-[(dihydro) pyrazolyl-3'-oxymethyene]-anilides, prepn. method and use thereof |
| CN1271348A (en) * | 1997-09-05 | 2000-10-25 | 巴斯福股份公司 | Method for producing (hetero) aromatic hydroxylamines |
| CN102399190A (en) * | 2011-12-20 | 2012-04-04 | 河南中医学院 | Pyraclostrobin and method for economically synthesizing same |
| CN103396364A (en) * | 2013-04-11 | 2013-11-20 | 南京理工大学 | N-alkyloxy-N-2-[1-(4-halogenated phenyl)-3-pyrazolyloxymethyl]phenylalkyl carbamate |
| CN104211641A (en) * | 2014-08-19 | 2014-12-17 | 山东康乔生物科技有限公司 | Synthetic technology for pyraclostrobin |
-
2016
- 2016-12-12 CN CN201611140585.2A patent/CN106632046A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154692A (en) * | 1994-07-06 | 1997-07-16 | 巴斯福股份公司 | 2-[(dihydro) pyrazolyl-3'-oxymethyene]-anilides, prepn. method and use thereof |
| CN1271348A (en) * | 1997-09-05 | 2000-10-25 | 巴斯福股份公司 | Method for producing (hetero) aromatic hydroxylamines |
| CN102399190A (en) * | 2011-12-20 | 2012-04-04 | 河南中医学院 | Pyraclostrobin and method for economically synthesizing same |
| CN103396364A (en) * | 2013-04-11 | 2013-11-20 | 南京理工大学 | N-alkyloxy-N-2-[1-(4-halogenated phenyl)-3-pyrazolyloxymethyl]phenylalkyl carbamate |
| CN104211641A (en) * | 2014-08-19 | 2014-12-17 | 山东康乔生物科技有限公司 | Synthetic technology for pyraclostrobin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107021927A (en) * | 2017-03-28 | 2017-08-08 | 天津大学 | A kind of pyraclostrobin crystal formation and preparation method thereof |
| CN108117521A (en) * | 2018-03-05 | 2018-06-05 | 安徽国星生物化学有限公司 | A kind of reversed recrystallization method of pyraclostrobin |
| CN110105287A (en) * | 2019-05-23 | 2019-08-09 | 江苏禾本生化有限公司 | A kind of synthesis technology of pyraclostrobin |
| CN110105287B (en) * | 2019-05-23 | 2022-04-26 | 江苏禾本生化有限公司 | Synthesis process of pyraclostrobin |
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