CN106699675B - A kind of Tebuconazole isomers is converted into the preparation method of Tebuconazole - Google Patents
A kind of Tebuconazole isomers is converted into the preparation method of Tebuconazole Download PDFInfo
- Publication number
- CN106699675B CN106699675B CN201611215656.0A CN201611215656A CN106699675B CN 106699675 B CN106699675 B CN 106699675B CN 201611215656 A CN201611215656 A CN 201611215656A CN 106699675 B CN106699675 B CN 106699675B
- Authority
- CN
- China
- Prior art keywords
- tebuconazole
- preparation
- isomers
- reaction
- highly basic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Abstract
The present invention relates to organic synthesis fields, and in particular to a kind of Tebuconazole isomers is converted into the preparation method of Tebuconazole.Tebuconazole is mainly used for preventing a variety of fungal diseases on the crops such as wheat, peanut, vegetables, banana, apple, and fungicidal spectrum is extensive, and activity is high, and the lasting period is long.In Tebuconazole production process, due to the generation of side reaction, produces a large amount of Tebuconazole isomers and give up admittedly, not only bring huge environmental protection pressure, but also reduce raw material availability, product yield is caused to reduce.For the present invention by under the Tebuconazole isomers reaction condition existing for high temperature, highly basic and catalyst that will detach, efficiently conversion obtains target product Tebuconazole, and content is up to 98% or more, 95% or more conversion yields.
Description
Technical field
The present invention relates to the preparation method that a kind of Tebuconazole isomers is converted into Tebuconazole, specifically Tebuconazole isomers exists
Under highly basic, high temperature and catalyst existence condition, Efficient Conversion is the method for Tebuconazole.
Background technology
(chemistry is entitled for Tebuconazole：(R, S) -1- (4- chlorphenyls) -4-4 dimethyl -3- (1H-1,2,4- triazol-1-yl first
Base) amyl- 3- alcohol) be Bayer A.G's exploitation triazole type low toxicity efficient germicide, be sterol demethylation inhibitors, it is wide
General head blight for preventing a variety of rust of cereal crop, powdery mildew, net blotch, root rot and wheat, the cercospora brown spot of peanut,
The gall of tea etc. of the gray mold of grape, the leaf spot of powdery mildew and banana and tea tree.Wherein, the Tebuconazole has following knot
Structure formula：
Tebuconazole can thoroughly prevent loose smut of barley, wheat net raw meat disease, the bunt smut of wheat and kind and pass as seed forming agent
Zonate spot.It is widely used in Europe, South and North America, global marketing volume was to have preferably more than 500,000,000 dollars in recent years
The pesticide species of development prospect.
During producing Tebuconazole, due to the generation of side reaction, produces a large amount of Tebuconazole isomers and give up admittedly, not only
Huge environmental protection pressure is brought, and reduces raw material availability, product yield is caused to reduce (reaction process such as following formula institute
Show).
Tebuconazole is the key product of our company, produces Tebuconazole per year and reaches 5000 tons or more, annual Tebuconazole isomers is deposited
Amount is big.It is badly in need of a kind of easy, high yield isomers method for transformation of exploitation, target product Tebuconazole is prepared, content reaches
98% or more.
Invention content
Invention broadly provides the preparation method that a kind of Tebuconazole isomers is converted into Tebuconazole, high temperature, highly basic with
And under catalyst existence condition, Tebuconazole isomers is converted into product Tebuconazole, and product content stably reaches 98% or more, improves
Raw material availability and total yield of products, there is a good prospects for commercial application.
The present invention is achieved by the following technical solutions：
A kind of Tebuconazole isomers is converted into the preparation method of Tebuconazole, characterized in that the synthesis road that the present invention is taken
Line is as follows, it is characterized in that：In this reaction, Tebuconazole isomers is converted into Tebuconazole under high temperature, highly basic, catalysts conditions.
Preferably：Solvent for use can be N,N-dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), toluene,
One or more of dimethylbenzene, ethylene glycol, cyclohexanol, methyl phenyl ethers anisole, more preferably n,N-Dimethylformamide, N- methylpyrroles
Alkanone.
Preferably：Selected highly basic can be lithium hydroxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxide, uncle
Sodium butoxide, potassium tert-butoxide, more preferably potassium hydroxide.
Preferably：The dosage of selected highly basic is that Tebuconazole isomers feeds intake the 0.1%-20%, more preferably 2- of equivalent
10%.
Preferably：Selected catalyst can be PEG, tetrabutylammonium bromide (TBAB), cetyl trimethyl bromination
The double octadecyldimethyl ammoniums of ammonium, dodecyl dimethyl benzyl ammonium chloride, bromination, Tebuconazole epoxy (structural formula I), 3- chloromethanes
Base -1- (4- chlorphenyls) -4,4- dimethyl -3- amylalcohols (formula II), 3- bromomethyls -1- (4- chlorphenyls) -4,4- dimethyl -
One or more of 3- amylalcohols (formula II I), more preferably 3- bromomethyls -1- (4- chlorphenyls) -4,4- dimethyl -3- penta
Alcohol (formula II I).
Preferably：The dosage of selected catalyst is that Tebuconazole isomers feeds intake the 0.1%-20% of equivalent, more preferably
1-10%.
Preferably：Selected temperature range is 80 DEG C -300 DEG C, more preferably 110 DEG C -180 DEG C.
Preferably：Selected reaction time range is 0.5-8h, more preferably 2-6h.
The solution have the advantages that：
1. the present invention adopts new technology, under conditions of high temperature, highly basic and catalyst, Tebuconazole isomers is converted into penta
Azoles alcohol, improves raw material availability, and the yield and content of product also significantly improve.
2. new process of the present invention is easy to operate, production security is high, while effectively reducing the discharge of solid waste.
Description of the drawings
Fig. 1 is the chemical equation that the method for the present invention Tebuconazole isomers is converted into Tebuconazole.
Specific implementation mode
The present invention is further described referring to specific embodiment, to more fully understand the present invention.
Embodiment 1
N,N-Dimethylformamide 120g is added in 250ml there-necked flasks, and Tebuconazole isomers 40g, potassium hydroxide is added
2.0g, 3- bromomethyl -1- (4- chlorphenyls) -4,4- dimethyl -3- amylalcohols 1.0g.It is warming up to 150 DEG C of reaction 4h.Sampling, measures
Tebuconazole 99.8%, isomers 0.2%.After precipitation, after adding water and toluene to be beaten, suction filtration obtains product Tebuconazole 38.6g, yield
96.5%, content 98.5%.
Embodiment 2
N-Methyl pyrrolidone 120g is added in 250ml there-necked flasks, and Tebuconazole isomers 40g, potassium hydroxide is added
5.0g, 3- chloromethyl -1- (4- chlorphenyls) -4,4- dimethyl -3- amylalcohols 2.0g.It is warming up to 180 DEG C of reaction 4h.Sampling, measures
Tebuconazole 99.7%, isomers 0.3%.After precipitation, after adding water and toluene to be beaten, suction filtration obtains product Tebuconazole 38.3g, yield
95.8%, content 98.2%.
Embodiment 3
N,N-Dimethylformamide 120g is added in 250ml there-necked flasks, and Tebuconazole isomers 40g, sodium hydroxide is added
3.0g, Tebuconazole epoxy 3.0g.It is warming up to 150 DEG C of reaction 4h.Sampling, measures Tebuconazole 99.8%, isomers 0.2%.Precipitation
Afterwards, after adding water and toluene to be beaten, suction filtration obtains product Tebuconazole 38.4g, yield 95.8%, content 98.2%.
Embodiment 4
In 250ml there-necked flasks be added dimethyl sulfoxide (DMSO) 120g, and be added Tebuconazole isomers 40g, sodium hydroxide 2.5g,
PEG20004.0g.It is warming up to 160 DEG C of reaction 4h.Sampling, measures Tebuconazole 99.6%, isomers 0.4%.After precipitation, add water and
After toluene mashing, suction filtration obtains product Tebuconazole 31.9g, yield 79.2%, content 98.0%.
Embodiment 5
N,N-Dimethylformamide 120g is added in 250ml there-necked flasks, and Tebuconazole isomers 40g, sodium hydroxide is added
2.0g、TBAB2.0g.It is warming up to 150 DEG C of reaction 4h.Sampling, measures Tebuconazole 99.7%, isomers 0.3%.After precipitation, add water
After being beaten with toluene, suction filtration obtains product Tebuconazole 33.5g, yield 83.2%, content 98.1%.
Embodiment 6
N,N-Dimethylformamide 120g is added in 250ml there-necked flasks, and Tebuconazole isomers 40g, sodium hydroxide is added
1.0g, 3- bromomethyl -1- (4- chlorphenyls) -4,4- dimethyl -3- amylalcohols 2.0g.It is warming up to 150 DEG C of reaction 4h.Sampling, measures
Tebuconazole 99.7%, isomers 0.3%.After precipitation, after adding water and toluene to be beaten, suction filtration obtains product Tebuconazole 38.4g, yield
95.2%, content 98.4%.
Embodiment 7
N,N-Dimethylformamide 120g is added in 250ml there-necked flasks, and Tebuconazole isomers 40g, sodium methoxide is added
2.0g, 3- bromomethyl -1- (4- chlorphenyls) -4,4- dimethyl -3- amylalcohols 3.0g.It is warming up to 150 DEG C of reaction 4h.Sampling, measures
Tebuconazole 99.5%, isomers 0.4%.After precipitation, after adding water and toluene to be beaten, suction filtration obtains product Tebuconazole 37.3g, yield
92.1%, content 98.1%.
Embodiment 8
Dimethylbenzene 120g is added in 250ml there-necked flasks, and Tebuconazole isomers 40g, potassium hydroxide 2.0g, 3- bromine first is added
Base -1- (4- chlorphenyls) -4,4- dimethyl -3- amylalcohols 2.0g.It is warming up to 150 DEG C of reaction 4h.Sampling, measures Tebuconazole
99.7%, isomers 0.3%.After precipitation, after adding water and toluene to be beaten, suction filtration obtains product Tebuconazole 38.4g, yield
94.5%, content 98.2%.
Embodiment 9
N,N-Dimethylformamide 120g is added in 250ml there-necked flasks, and Tebuconazole isomers 40g, potassium tert-butoxide is added
2.0g, 3- bromomethyl -1- (4- chlorphenyls) -4,4- dimethyl -3- amylalcohols 2.0g.It is warming up to 150 DEG C of reaction 4h.Sampling, measures
Tebuconazole 99.7%, isomers 0.3%.After precipitation, after adding water and toluene to be beaten, suction filtration obtains product Tebuconazole 37.6g, yield
92.5%, content 98.2%.
Specific embodiments of the present invention are described in detail above, but it is intended only as example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
It substitutes also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by impartial conversion and
Modification, all should be contained within the scope of the invention.
Claims (14)
1. a kind of Tebuconazole isomers is converted into the preparation method of Tebuconazole, chemical equation is as follows:
It is characterized in that：In this reaction, Tebuconazole is different
Structure body is converted into Tebuconazole under high temperature, highly basic, catalysts conditions, and the catalyst is Tebuconazole epoxy (structural formula I), 3- chlorine
Methyl-1-(4- chlorphenyls)-4,4- dimethyl-3- amylalcohols (formula II), 3- bromomethyls-1- (4- chlorphenyls)-4,4- diformazans
One or more of base -3- amylalcohols (formula II I),
2. preparation method according to claim 1, it is characterized in that：Solvent for use is N, N- dimethyl formyls in the reaction
One or more of amine, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, ethylene glycol, cyclohexanol, methyl phenyl ethers anisole.
3. preparation method according to claim 2, it is characterized in that：Solvent for use is N,N-dimethylformamide or N- methyl
Pyrrolidones.
4. preparation method according to claim 1, it is characterized in that：The highly basic is lithium hydroxide, calcium hydroxide, hydrogen-oxygen
Change sodium, potassium hydroxide, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide.
5. preparation method according to claim 1, it is characterized in that：The highly basic is potassium hydroxide.
6. preparation method according to claim 1, it is characterized in that：The dosage of the highly basic is that Tebuconazole isomers feeds intake
The 0.1%-20% of equivalent.
7. preparation method according to claim 6, it is characterized in that：The dosage of the highly basic is that Tebuconazole isomers feeds intake
The 2-10% of equivalent.
8. preparation method according to claim 1, it is characterized in that：The catalyst is 3- bromomethyls -1- (4- chlorobenzenes
Base) -4,4- dimethyl -3- amylalcohols (formula II I).
9. preparation method according to claim 1, it is characterized in that：The dosage of the catalyst is that Tebuconazole isomers feeds intake
The 0.1%-20% of equivalent.
10. preparation method according to claim 9, it is characterized in that：The dosage of the catalyst is that Tebuconazole isomers is thrown
Expect that equivalent is 1-10%.
11. preparation method according to claim 1, it is characterized in that：The temperature range of the reaction is 80 DEG C -300 DEG C.
12. preparation method according to claim 11, it is characterized in that：The temperature range of the reaction is 110 DEG C -180 DEG C.
13. preparation method according to claim 1, it is characterized in that：The reaction time range of the reaction is 0.5-8h.
14. preparation method according to claim 13, it is characterized in that：The reaction time range of the reaction is 2-6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611215656.0A CN106699675B (en) | 2016-12-26 | 2016-12-26 | A kind of Tebuconazole isomers is converted into the preparation method of Tebuconazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611215656.0A CN106699675B (en) | 2016-12-26 | 2016-12-26 | A kind of Tebuconazole isomers is converted into the preparation method of Tebuconazole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106699675A CN106699675A (en) | 2017-05-24 |
| CN106699675B true CN106699675B (en) | 2018-08-07 |
Family
ID=58896108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611215656.0A Active CN106699675B (en) | 2016-12-26 | 2016-12-26 | A kind of Tebuconazole isomers is converted into the preparation method of Tebuconazole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106699675B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112020009870A2 (en) * | 2017-11-17 | 2020-11-03 | East China University Of Science And Technology | polymorph of tebuconazole and method of preparing it |
| CN112010812A (en) * | 2020-09-17 | 2020-12-01 | 江苏七洲绿色化工股份有限公司 | Transposition method of 3, 3-dimethyl-1- (1H-1,3, 4-triazole-1-yl) butan-2-one |
| CN113582979B (en) * | 2021-08-20 | 2023-02-24 | 浙江禾本科技股份有限公司 | Method for synthesizing propiconazole from isomers |
| CN117143934A (en) * | 2023-07-18 | 2023-12-01 | 常州大学 | Method for preparing (R) -tebuconazole by enzyme chemical method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4639527A (en) * | 1983-11-25 | 1987-01-27 | Bayer Aktiengesellschaft | Process for the preparation of β-hydroxyethyl-(1,2,4-triazole) derivatives |
| CN102276541A (en) * | 2010-06-11 | 2011-12-14 | 南通派斯第农药化工有限公司 | Preparation method of 1-(4-chlorophenyl)-3-(1-H-1,2,4-triazolyl-1-methyl)-4,4-dimethyl pentan-3-ol |
-
2016
- 2016-12-26 CN CN201611215656.0A patent/CN106699675B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4639527A (en) * | 1983-11-25 | 1987-01-27 | Bayer Aktiengesellschaft | Process for the preparation of β-hydroxyethyl-(1,2,4-triazole) derivatives |
| CN102276541A (en) * | 2010-06-11 | 2011-12-14 | 南通派斯第农药化工有限公司 | Preparation method of 1-(4-chlorophenyl)-3-(1-H-1,2,4-triazolyl-1-methyl)-4,4-dimethyl pentan-3-ol |
Non-Patent Citations (1)
| Title |
|---|
| 杀菌剂戊唑醇的合成及表征;谭成侠、张谦;《高校化学工程学报》;20071231;第21卷(第6期);第1030-1033页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106699675A (en) | 2017-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106699675B (en) | A kind of Tebuconazole isomers is converted into the preparation method of Tebuconazole | |
| CN102239137B (en) | Novel pyrazole-4-N-alkoxycarboxamides as microbiocides | |
| CN105130757B (en) | A kind of chlorine 3 of epoxiconazole intermediate 1（2 chlorobenzenes）‑2‑（4 fluorobenzene）The synthesis technique of 2 propyl alcohol | |
| CA1128528A (en) | Hydroxyethyl-azole compounds, their production and their medicinal use | |
| CN102060850B (en) | Preparing and refining methods of difenoconazole | |
| GB2129000A (en) | Fungicidal azole compounds | |
| DE2324010B2 (en) | 1-Substituted 2-triazolyl-2-phenoxyethanol compounds, process for their preparation and their use for combating fungi | |
| CN106588791A (en) | Novel technology for synthesizing bactericide tebuconazole without solvent | |
| CN101899040A (en) | Preparation process of difenoconazole | |
| CN102225935A (en) | Manufacturing method of proPiconazole | |
| CN104529917A (en) | Synthetic method for bactericide tebuconazole | |
| JPS6089477A (en) | Novel azole compound | |
| CN102432600B (en) | Purification method of difenoconazole | |
| CN109336848B (en) | Tebuconazole intermediate and preparation method of tebuconazole | |
| DE3234627A1 (en) | SUBSTITUTED AZOLYLALKYL T-BUTYL KETONES AND CARBINOLS | |
| US4489085A (en) | Antimicrobial agents and their use employing imidazolyl-enal ethers | |
| CN103664809B (en) | A kind of preparation method of paclobutrazol | |
| CN102276541B (en) | Preparation method of 1-(4-chlorophenyl)-3-(1-H-1,2,4-triazolyl-1-methyl)-4,4-dimethyl pentan-3-ol | |
| US4207328A (en) | 1-Phenoxy-2-(2,4-dichlorophenyl)-1-imidazol-1-yl-ethan-2-ones and -ols and antimycotic and fungicidal use | |
| CN109867640A (en) | A kind of preparation method of fumidil amido alcohol | |
| CN102304032B (en) | Method for preparing tebuconazole intermediate | |
| IE57412B1 (en) | Antifungal triazole derivatives | |
| CN104998648A (en) | A nickel, copper, zinc supported mesoporous MnO2catalyst and its preparation method of 4, 4-dimethyl-1-(4-p-chlorophenyl)-3-pentanone | |
| CN102993109A (en) | Preparation method of amidine compound | |
| US4284639A (en) | Combating fungi with 1-phenoxy-2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-ones and -ols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |