CN108863916A - A kind of ZEN 90160 new technique for synthesizing - Google Patents
A kind of ZEN 90160 new technique for synthesizing Download PDFInfo
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- CN108863916A CN108863916A CN201810599967.4A CN201810599967A CN108863916A CN 108863916 A CN108863916 A CN 108863916A CN 201810599967 A CN201810599967 A CN 201810599967A CN 108863916 A CN108863916 A CN 108863916A
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- ether
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- trifluoromethyl pyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention relates to a kind of ZEN 90160 new technique for synthesizing.By the fluoro- 5- trifluoromethyl pyridine reaction of the potassium hydroxide aqueous solution and 2- that will measure, hydrofluoric acid is neutralized, is filtered, and washing, drying obtains trifluoromethyl pyridine alcohol；Then it reacts DMF, trifluoromethyl pyridine alcohol, o-chloromethyl methyl acetate and sodium hydroxide to obtain ether-ether；Then toluene, ether-ether, methyl formate and sodium hydroxide reaction precipitation are obtained into enol；Finally methylene chloride, enol, dimethyl suflfate and sodium hydroxide are reacted, filtered, drying, ZEN 90160 finished product is obtained, entire reaction condition is mild, easy to operate, it is a kind of more satisfactory industrializing synthesis route, synthesis total recovery reaches 65% or more, and product content reaches 97%.
Description
Technical field
The invention belongs to ZEN 90160 production technical field more particularly to a kind of ZEN 90160 new technique for synthesizing.
Background technique
ZEN 90160 is systemic fungicide, controlling object wide spectrum, and the foliage disease such as leaf for being mainly used for preventing and treating wheat is withered
Disease, leaf rust, glume blight, brown spot, powdery mildew etc., compared with other methoxy acrylic bactericides, ZEN 90160 pair
Wheat leaf blessing disease, net blotch and moire disease have stronger therapeutic effect.ZEN 90160 is by Syngenta Co., Ltd in 2001 in Europe
It releases, 2006, the product was purchased by E.I.Du Pont Company, while its insecticide Rynaxypyr (health is wide) right to use being licensed to
Syngenta.Thereafter E.I.Du Pont Company is by this product in Latin America, the registration of the markets such as North America.ZEN 90160 is on Argentina, ground difficult to understand
Benefit, Belgium, Brazil, Colombia, Czech Republic, Denmark, Estonia, Finland, France, Germany, Hungary, Ai Er
Orchid, Kenya, Latvia, Lithuania, Holland, New Zealand, Norway, Poland, Romania, Slovakia, South Africa, Sweden,
The registration of the ground such as Britain, in the U.S., Italian and Portuguese registration is in progress.The estimated ZEN 90160 of E.I.Du Pont Company has 1.5
Hundred million dollars of market potential.
It sells in the year in the new and effective fungicide ZEN 90160 whole world more than 100,000,000 dollars, market also in continuous increase, is
It is maintained at the sustainable development in disinfectant use in agriculture market, new profit point is created for enterprise, Products types is enriched, to it
Synthesis technology has carried out successful exploitation, provides a kind of ZEN 90160 new technique for synthesizing.
Summary of the invention
The present invention is to solve well-known technique and provide a kind of ZEN 90160 new technique for synthesizing.
The present invention is adopted the technical scheme that solve well-known technique：A kind of ZEN 90160 conjunction
At new process, include the following steps：
Step 1：Reaction is added in 50 parts of potassium hydroxide aqueous solution and the fluoro- 5- trifluoromethyl pyridine of 25 parts of 2- first
Reaction is hydrolyzed in stirring heating in kettle, and sequentially adds hydrofluoric acid neutralization, then by filtering, washing, drying obtains trifluoro pyrrole
Pyridine alcohol；
Step 2：By the o-chloromethyl methyl acetate of the same number of trifluoromethyl pyridine alcohol in step 1, sodium hydroxide and
DMF, which is added together in reaction kettle, to carry out the first condensation reaction and generates ether-ether, and reaction solution is successively carried out to washing process and is taken off
Molten processing obtains ether-ether；
Step 3：25 parts of toluene, 25 parts of methyl formates and 25 parts of sodium hydroxide mixed solutions are added in ether-ether in step 2
Second of condensation reaction of middle progress, successively carries out washing process for reaction solution and carrying out precipitation treatment obtains enol；
Step 4：Enol obtained in step 3 is sequentially added into 25 parts of methylene chloride, 25 parts of dimethyl suflfates and 25 parts
Sodium hydroxide carries out third time condensation reaction, generates ZEN 90160；
Step 5：By the mixed solution in step 4, washing process and carrying out precipitation treatment are successively carried out, is carrying out low temperature crystallization
Processing, is finally filtered, dries, and pure ZEN 90160 crystallization can be obtained, and purity is greater than 97%.
In the present invention, the concentration of the potassium hydroxide aqueous solution is 50%.
In the present invention, reaction solution is added acid and neutralized by the pure and mild potassium fluoride of the trifluoromethyl pyridine generated in the step 1, and mistake
Trifluoromethyl pyridine alcohol is filtered, a large amount of potassium fluoride solution can be recycled, and the content of potassium fluoride solution is greater than 65%.
The present invention has the advantage that as follows with good effect：
1. a kind of ZEN 90160 new technique for synthesizing proposed by the present invention, passes through the potassium hydroxide aqueous solution and 2- that will be measured
Fluoro- 5- trifluoromethyl pyridine (abbreviation fluoride) reaction, hydrofluoric acid are neutralized, are filtered, and washing, drying obtains trifluoromethyl pyridine alcohol, connects
React DMF, trifluoromethyl pyridine alcohol, o-chloromethyl methyl acetate and sodium hydroxide to obtain ether-ether, then by toluene, ether-ether,
Methyl formate and sodium hydroxide reaction precipitation obtain enol, finally by methylene chloride, enol, dimethyl suflfate and sodium hydroxide
Reaction is filtered, and drying obtains ZEN 90160 finished product, and entire reaction condition is mild, easy to operate, is a kind of more satisfactory
Industrializing synthesis route, synthesis total recovery reach 65% or more, and product content reaches 97%.
Detailed description of the invention
Fig. 1 is of the inventionTrifluoromethyl pyridine alcohol schematic diagram
Fig. 2It is of the inventionEther-ether schematic diagram
Fig. 3It is of the inventionEnol schematic diagram
Fig. 4It is of the inventionZEN 90160 schematic diagram
Fig. 5It is of the inventionZEN 90160 crystallizes schematic diagram
Specific embodiment
In order to further understand the content, features and effects of the present invention, hereby enumerating following embodiment, and cooperate attached
Detailed description are as follows for figure.
A kind of ZEN 90160 new technique for synthesizing of the invention, includes the following steps：
Step 1：Reaction is added in 50 parts of potassium hydroxide aqueous solution and the fluoro- 5- trifluoromethyl pyridine of 25 parts of 2- first
Reaction is hydrolyzed in stirring heating in kettle, and sequentially adds hydrofluoric acid neutralization, then by filtering, washing, drying obtains trifluoro pyrrole
Pyridine alcohol；
Wherein：Key reaction equation such as Fig. 1：
Step 2：By the o-chloromethyl methyl acetate of the same number of trifluoromethyl pyridine alcohol in step 1, sodium hydroxide and
DMF, which is added together in reaction kettle, to carry out the first condensation reaction and generates ether-ether, and reaction solution is successively carried out to washing process and is taken off
Molten processing obtains ether-ether；
Wherein：Key reaction equation such as Fig. 2：
Step 3：25 parts of toluene, 25 parts of methyl formates and 25 parts of sodium hydroxide mixed solutions are added in ether-ether in step 2
Second of condensation reaction of middle progress, successively carries out washing process for reaction solution and carrying out precipitation treatment obtains enol；
Wherein：Key reaction equation such as Fig. 3：
Step 4：Enol obtained in step 3 is sequentially added into 25 parts of methylene chloride, 25 parts of dimethyl suflfates and 25 parts
Sodium hydroxide carries out third time condensation reaction, generates ZEN 90160；
Wherein：Key reaction equation such as Fig. 4：
Step 5：By the mixed solution in step 4, washing process and carrying out precipitation treatment are successively carried out, then carry out low temperature crystallization
Processing, is finally filtered, dries, and pure ZEN 90160 crystallization can be obtained, and purity is greater than 97%.
In the present invention, the concentration of the potassium hydroxide aqueous solution is 50%.
In the present invention, potassium hydroxide is added acid and neutralized by the pure and mild potassium fluoride of the trifluoromethyl pyridine generated in the step 1, and
Trifluoromethyl pyridine alcohol is filtered out, a large amount of potassium fluoride solution can be recycled, and the content of potassium fluoride solution is greater than 65%.
Whole flow process such as Fig. 5
The above is only the preferred embodiments of the present invention, and is not intended to limit the present invention in any form,
Any simple modification made to the above embodiment according to the technical essence of the invention, equivalent variations and modification, belong to
In the range of technical solution of the present invention.
Claims (3)
1. a kind of ZEN 90160 new technique for synthesizing, it is characterised in that：Include the following steps：
Step 1：50 parts of potassium hydroxide aqueous solution and the fluoro- 5- trifluoromethyl pyridine of 25 parts of 2- are added in reaction kettle and are stirred first
It mixes heating and reaction is hydrolyzed, and sequentially add hydrofluoric acid neutralization, then by filtering, washing dries and obtains trifluoromethyl pyridine alcohol；
Step 2：Together by o-chloromethyl methyl acetate, sodium hydroxide and the DMF of the same number of trifluoromethyl pyridine alcohol in step 1
It is added and carries out the first condensation reaction in reaction kettle and generate ether-ether, reaction solution is successively subjected to washing process and carrying out precipitation treatment obtains
To obtaining ether-ether；
Step 3：By ether-ether in step 2 be added 25 parts of toluene, in 25 parts of methyl formates and 25 parts of sodium hydroxide mixed solutions into
Reaction solution is successively carried out washing process and carrying out precipitation treatment obtains enol by second of condensation reaction of row；
Step 4：Enol obtained in step 3 is sequentially added into 25 parts of methylene chloride, 25 parts of dimethyl suflfates and 25 parts of hydrogen-oxygens
Change sodium and carry out third time condensation reaction, generates ZEN 90160；
Step 5：By the mixed solution in step 4, washing process and carrying out precipitation treatment are successively carried out, then carry out low temperature crystallization processing,
It is finally filtered, dries, pure ZEN 90160 crystallization can be obtained, purity is greater than 97%.
2. a kind of ZEN 90160 new technique for synthesizing according to claim 1, which is characterized in that the potassium hydroxide aqueous solution
Concentration be 50%.
3. a kind of ZEN 90160 new technique for synthesizing according to claim 1, which is characterized in that generated in the step 1
Reaction solution is added acid and neutralized, and filters out trifluoromethyl pyridine alcohol by the pure and mild potassium fluoride of trifluoromethyl pyridine, can recycle a large amount of potassium fluoride
Solution, and the content of potassium fluoride solution is greater than 65%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810599967.4A CN108863916A (en) | 2018-06-11 | 2018-06-11 | A kind of ZEN 90160 new technique for synthesizing |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679422A (en) * | 2020-12-30 | 2021-04-20 | 锦州三丰科技有限公司 | Preparation method of picoxystrobin |
| CN112707861A (en) * | 2020-12-30 | 2021-04-27 | 锦州三丰科技有限公司 | Method for preparing 2- (6-trifluoromethyl pyridine-2-yloxymethyl) methyl phenylacetate |
| CN113185455A (en) * | 2020-01-14 | 2021-07-30 | 新发药业有限公司 | Preparation method of 2-hydroxy-6-trifluoromethylpyridine |
-
2018
- 2018-06-11 CN CN201810599967.4A patent/CN108863916A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185455A (en) * | 2020-01-14 | 2021-07-30 | 新发药业有限公司 | Preparation method of 2-hydroxy-6-trifluoromethylpyridine |
| CN112679422A (en) * | 2020-12-30 | 2021-04-20 | 锦州三丰科技有限公司 | Preparation method of picoxystrobin |
| CN112707861A (en) * | 2020-12-30 | 2021-04-27 | 锦州三丰科技有限公司 | Method for preparing 2- (6-trifluoromethyl pyridine-2-yloxymethyl) methyl phenylacetate |
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Application publication date: 20181123 |