CN109705048A - A kind of clean method for preparing of Tebuconazole - Google Patents
A kind of clean method for preparing of Tebuconazole Download PDFInfo
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- CN109705048A CN109705048A CN201910100105.7A CN201910100105A CN109705048A CN 109705048 A CN109705048 A CN 109705048A CN 201910100105 A CN201910100105 A CN 201910100105A CN 109705048 A CN109705048 A CN 109705048A
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Abstract
The invention belongs to technical field of organic synthesis, more particularly to a kind of clean method for preparing of Tebuconazole, it is the following steps are included: S1: being added 1 into a reaction vessel, 2,4- triazoles, inorganic base, and the diethylene glycol monomethyl ether as solvent, after heating, reaction raw materials A is slowly added dropwise, then insulation reaction；S2: after fully reacting, cooling is stood, is post-processed to get target product Tebuconazole.The mother liquor post-processed in the clean method for preparing of the Tebuconazole can continue to be applied in lower batch reaction liquid, the conversion ratio without influencing reaction yield and reaction raw materials A；Therefore, solvent post-processes simple and easy without recycling.Also, the total recovery of the clean method for preparing of the Tebuconazole is up to 91% or more, and therefore Tebuconazole product purity, shows higher industrial application value up to 98%.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of clean method for preparing of Tebuconazole.
Background technique
Tebuconazole is Bayer A.G in the triazole bactericidal agent of exploitation in 1986.The structural formula of Tebuconazole is as follows:
It is a kind of ergosterol demethylation inhibitors, has and protects, treats, rooting out three zones, and has efficient
Low toxicity and wide spectrum characteristic, not only activity is high, but also the lasting period is long, includes that monocotyledon and dicotyledon are pacified to many crops
Entirely；It is mainly used for seed treatment and foliar spray on the crops such as wheat, vegetables, banana, apple, is more satisfactory at present
Fungicide, have a extensive future, thus receive significant attention.
End in December, 2016, the country, China registers Original Tebuconazole 51, single dose 284, mixture 234 altogether.From mesh
The registration situation in preceding China sees that the potentiality of Tebuconazole, which are not yet received, to be given full play to, and the activity based on Tebuconazole is high, dosage is few, anti-
The features such as spectrum is wide is controlled, with going deep into for research, Tebuconazole will obtain further developing and paying attention to.
The synthetic method and technique of a series of Tebuconazoles are reported in the prior art.For example, document " penta azoles of new type bactericide
The synthesis technology of alcohol " (Agriculture of Anhui science, 2007,144-192) disclose a kind of synthetic method of Tebuconazole, use highly basic
Property ion exchange resin makees basic catalyst, and using butanol as solvent, solves target compound using catalysts selective and contain
Relatively low defect is measured, the isomers isotebuconazole content in target compound is reduced；According to penta azoles made from the synthetic method
Alcohol product purity is 98.2%, but total recovery is only 67%, it is seen then that its product yield is low, is unfavorable for large-scale industrial production.
For another example, document " synthesis and characterization of Tebucomazole in high purity " (pesticide, 2006,397-398) discloses another kind penta
Azoles alcohol preparation process, specifically using sodium methoxide as catalyst, dimethylbenzene is solvent, is heated up under agitation and slow into feed liquid
It is passed through dry CO2Gas；After completion of the reaction, feed liquid is cooled to 60 DEG C, a certain amount of water is added and carries out washing layering, it will be organic
The Tebuconazole crude product that content 88%~90% is arrived after solvent is mutually evaporated, crude product carries out recrystallizing and can obtaining in specific solvent
To the Tebuconazole fine work of purity 95%, yield 83.4%.However, the complex operation, and gained Tebuconazole product must be through two
Secondary purification, to cause " three wastes " amount excessive.
It can be seen that the Tebuconazole synthesis technology provided in the prior art, most of all to there is many engineerings and technique side
The technological deficiency in face, if reaction yield is low, products obtained therefrom needs secondary refining, the recycling of reaction dissolvent difficulty etc., to cannot achieve penta
It is prepared by the cleaning of azoles alcohol.
Summary of the invention
Technical solution provided by the present invention is intended to provide a kind of new process for preparing Tebuconazole, uses " cooking different foods in one pot " side
Method, operating procedure is simple, and solvent can directly apply reaction, therefore industrial application value with higher without recycling.
Specifically, the invention discloses a kind of clean method for preparing of Tebuconazole, synthetic route is as follows:
Also, the clean method for preparing the following steps are included:
S1: 1,2,4- triazoles, inorganic base, and the diethylene glycol list first as solvent are added into a reaction vessel
After heating, reaction raw materials A is slowly added dropwise, then insulation reaction in ether；
S2: after fully reacting, cooling is stood, is post-processed to get target product Tebuconazole.
Wherein, reaction raw materials A can be synthesized according to the preparation method introduced in the prior art, therefore herein not
It repeats again.
Preferably, in the clean method for preparing of above-mentioned Tebuconazole, the inorganic base is selected from following any one or more
Combination: potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide.On this basis, the inorganic base is further preferred
For potassium hydroxide or sodium hydroxide.
Preferably, in the clean method for preparing of above-mentioned Tebuconazole, the mole of the inorganic base is the reaction raw materials A
0.1~1.5 times of mole.It is further preferred that the mole of the inorganic base is the mole of the reaction raw materials A
0.2~0.5 times.
Preferably, in the clean method for preparing of above-mentioned Tebuconazole, the quality of the diethylene glycol monomethyl ether is described anti-
0.5~10.0 times of quality for answering raw material A.It is further preferred that the quality of the diethylene glycol monomethyl ether is the reaction raw materials A
2~5 times of quality.
Preferably, in the clean method for preparing of above-mentioned Tebuconazole, the duration that the reaction raw materials A is slowly added dropwise is
0.5~5 hour, further preferably 1~3 hour.
Preferably, in the clean method for preparing of above-mentioned Tebuconazole, the temperature of the insulation reaction is 100~135 DEG C, into
One step is preferably 105~110 DEG C.
Preferably, in the clean method for preparing of above-mentioned Tebuconazole, the duration of the insulation reaction is 5~15 small
When.It is further preferred that the duration of the insulation reaction is 8~10 hours.
Preferably, in the clean method for preparing of above-mentioned Tebuconazole, it is described post-processing the following steps are included:
It filters, takes filter cake, elute filter cake with low polar organic solvent, it is dry.
It is further preferred that the low polar organic solvent is selected from following in the clean method for preparing of above-mentioned Tebuconazole
Any one or more combination: n-hexane, hexamethylene, toluene, benzene, carbon tetrachloride, petroleum ether.
In short, the clean method for preparing of Tebuconazole provided by the present invention has the advantages that
The mother liquor post-processed in the clean method for preparing of the Tebuconazole can continue to be applied in lower batch reaction liquid,
Conversion ratio without influencing reaction yield and reaction raw materials A；Therefore, solvent post-processes simple and easy without recycling.Also, institute
The total recovery of the clean method for preparing of Tebuconazole is stated up to 91% or more, and Tebuconazole product purity is up to 98%, therefore, show compared with
High industrial application value.
Specific embodiment
The present invention is further elaborated With reference to embodiment, but the present invention is not limited to following embodiment party
Formula.
In a preferred embodiment, Tebuconazole clean method for preparing comprising the following specific steps
S1: being added 1,2,4- triazoles into a reaction vessel, potassium hydroxide, diethylene glycol monomethyl ether, after heating, slowly
Dropwise reaction raw material A, then insulation reaction；
S2: after fully reacting, standing cooling, filter, take filter cake, elutes filter cake with n-hexane, dry to get target product
Tebuconazole.
In a further preferred embodiment, the mole of the potassium hydroxide is mole of the reaction raw materials A
0.1~1.5 times of amount.
In a further preferred embodiment, the quality of the diethylene glycol monomethyl ether is the reaction raw materials A's
0.5~10.0 times of quality.
In a further preferred embodiment, the duration that the reaction raw materials A is slowly added dropwise is 0.5~5 small
When.
In a further preferred embodiment, the temperature of the insulation reaction is 100~135 DEG C.
In a further preferred embodiment, the duration of the insulation reaction is 5~15 hours.
In a further advantageous embodiment, Tebuconazole clean method for preparing comprising the following specific steps
S1: being added 1,2,4- triazoles into a reaction vessel, sodium hydroxide, diethylene glycol monomethyl ether, after heating, slowly
Dropwise reaction raw material A, then insulation reaction；
S2: after fully reacting, standing cooling, filter, take filter cake, elutes filter cake with hexamethylene, dry to get target product
Tebuconazole.
In a further advantageous embodiment, Tebuconazole clean method for preparing comprising the following specific steps
S1: 1,2,4- triazoles, potassium carbonate being added into a reaction vessel, and diethylene glycol monomethyl ether after heating, slowly drips
Add reaction raw materials A, then insulation reaction；
S2: after fully reacting, standing cooling, filter, take filter cake, elutes filter cake with n-hexane and petroleum ether mixed solvent,
Drying is to get target product Tebuconazole.
Step in the preparation method of following Tebuconazoles is routine operation unless otherwise instructed, and used reaction is former
Material, reagent can obtain unless otherwise instructed from public commercial source.
Embodiment 1
Into 500ml there-necked flask, be added 1,2,4- triazole of 20.5g, and be added 100.0g diethylene glycol monomethyl ether and
6.5g potassium hydroxide, oil bath heating control interior temperature at 100~105 DEG C；Then, 60.0g reaction raw materials A is slowly added dropwise, dropwise addition is held
The continuous time is 2h, and drop finishes, and the insulated and stirred 10h at 100~110 DEG C, TLC monitor reaction raw materials A fully reacting.Then, will
Reaction solution standing is cooled to room temperature, and ice-water bath keeps the temperature 1h, is filtered, and the mother liquor of suction filtration is collected rear enclosure and used, and takes filter cake, with 50ml just oneself
Alkane elution, vacuum drying obtain Tebuconazole product quality 67.9g, purity 98.0%, total recovery 91.0%.The Tebuconazole product
It is characterized as below: GCMS (M+): 307.2 [6], 274.1 [6], 250.1 [100], 207.1 [11], 163.1 [14], 125.1
[100],103.1[12],83.1[37]。1HNMR(CDCl3): 8.23 (s, 1H), 8.03 (s, 1H), 7.21 (d, 2H, J=
8.0Hz), 6.97 (d, 2H, J=8.0Hz), 4.37 (s, 2H), 3.07 (s, 1H), 2.43-2.50 (m, 1H), 1.68-1.88 (m,
3H),1.05(s,9H)。
Embodiment 2
Into 500ml there-necked flask, be added 1,2,4- triazole of 21.0g, and be added 150.0g diethylene glycol monomethyl ether and
7.0g potassium hydroxide, oil bath heating control interior temperature at 100~110 DEG C；Then, 60.0g reaction raw materials A is slowly added dropwise, dropwise addition is held
The continuous time is 1h, and drop finishes, and the insulated and stirred 10h at 100~120 DEG C, TLC monitor reaction raw materials A fully reacting.Then, will
Reaction solution standing is cooled to room temperature, and ice-water bath keeps the temperature 1h, is filtered, and the mother liquor of suction filtration is collected rear enclosure and used, and takes filter cake, with 50ml just oneself
The elution of the mixed solvent of alkane and petroleum ether, vacuum drying obtain Tebuconazole product quality 68.6g, purity 98.2%, total recovery
92.1%.The Tebuconazole product characterizes data consistent with Example 1.
Embodiment 3
Into 500ml there-necked flask, be added 1,2,4- triazole of 21.0g, and be added 120.0g diethylene glycol monomethyl ether and
7.5g potassium hydroxide, oil bath heating control interior temperature at 100~105 DEG C；Then, 60.0g reaction raw materials A is slowly added dropwise, dropwise addition is held
The continuous time is 0.5h, and drop finishes, and the insulated and stirred 10h at 100~105 DEG C, TLC monitor reaction raw materials A fully reacting.Then,
Reaction solution standing is cooled to room temperature, ice-water bath keeps the temperature 1h, filters, and the mother liquor of suction filtration is collected rear enclosure and used, and filter cake is taken, with 50ml ring
Hexane, vacuum drying, obtains Tebuconazole product quality 68.1g, purity 98.1%, total recovery 91.3%.The Tebuconazole produces
Product characterize data is the same as embodiment 1.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (9)
1. a kind of clean method for preparing of Tebuconazole, which is characterized in that its synthetic route is as follows:
Also, the clean method for preparing the following steps are included:
S1: 1,2,4- triazoles, inorganic base are added into a reaction vessel, and as the diethylene glycol monomethyl ether of solvent, adds
After heat, reaction raw materials A is slowly added dropwise, then insulation reaction；
S2: after fully reacting, cooling is stood, is post-processed to get target product Tebuconazole.
2. the clean method for preparing of Tebuconazole according to claim 1, which is characterized in that the inorganic base is selected from following
One or more combination: potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide.
3. the clean method for preparing of Tebuconazole according to claim 1, which is characterized in that the mole of the inorganic base is
0.1~1.5 times of the mole of the reaction raw materials A.
4. the clean method for preparing of Tebuconazole according to claim 1, which is characterized in that the diethylene glycol monomethyl ether
Quality is 0.5~10.0 times of quality of the reaction raw materials A.
5. the clean method for preparing of Tebuconazole according to claim 1, which is characterized in that the reaction raw materials are slowly added dropwise
The duration of A is 0.5~5 hour.
6. the clean method for preparing of Tebuconazole according to claim 1, which is characterized in that the temperature of the insulation reaction is
100~135 DEG C.
7. the clean method for preparing of Tebuconazole according to claim 1, which is characterized in that the insulation reaction it is lasting when
Between be 5~15 hours.
8. the clean method for preparing of Tebuconazole according to claim 1, which is characterized in that the post-processing includes following step
It is rapid:
It filters, takes filter cake, elute filter cake with low polar organic solvent, it is dry.
9. the clean method for preparing of Tebuconazole according to claim 8, which is characterized in that the low polar organic solvent choosing
From following any one or more combination: n-hexane, hexamethylene, toluene, benzene, carbon tetrachloride, petroleum ether.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253328A (en) * | 2020-03-26 | 2020-06-09 | 江苏七洲绿色化工股份有限公司 | Preparation method of tebuconazole |
| CN115260110A (en) * | 2022-08-12 | 2022-11-01 | 辽宁众辉生物科技有限公司 | Green and efficient synthesis method of tebuconazole |
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| CN101130522A (en) * | 2006-08-22 | 2008-02-27 | 上海生农生化制品有限公司 | Novel method for synthesizing fungicide tebuconazole |
| CN103588730A (en) * | 2013-11-14 | 2014-02-19 | 江苏剑牌农化股份有限公司 | Synthetic method for preparing triazole fungicide type (III) compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130522A (en) * | 2006-08-22 | 2008-02-27 | 上海生农生化制品有限公司 | Novel method for synthesizing fungicide tebuconazole |
| CN103588730A (en) * | 2013-11-14 | 2014-02-19 | 江苏剑牌农化股份有限公司 | Synthetic method for preparing triazole fungicide type (III) compound |
Non-Patent Citations (2)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253328A (en) * | 2020-03-26 | 2020-06-09 | 江苏七洲绿色化工股份有限公司 | Preparation method of tebuconazole |
| CN115260110A (en) * | 2022-08-12 | 2022-11-01 | 辽宁众辉生物科技有限公司 | Green and efficient synthesis method of tebuconazole |
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