CN105061406A - Preparation technology of difenoconazole technical material - Google Patents
Preparation technology of difenoconazole technical material Download PDFInfo
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- CN105061406A CN105061406A CN201510418498.8A CN201510418498A CN105061406A CN 105061406 A CN105061406 A CN 105061406A CN 201510418498 A CN201510418498 A CN 201510418498A CN 105061406 A CN105061406 A CN 105061406A
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- difenoconazole
- preparation technology
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- chlorophenoxy
- dioxolane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation technology of a difenoconazole technical material. The preparation technology is characterized by specially comprising reaction steps as follows: placing 2-bromomethyl-2-(2-chloro-4-(4-chlorophenoxy)phenyl)-4-methyl-1,3-dioxolane, cyclohexane and n-butyl ammonium bromide into a reaction kettle, keeping the temperature to range from 35 DEG C to 45 DEG C, dropwise adding hydrazine hydrate for 3-4 h, keeping the temperature for 2-3 h after addition, performing sampling detection, after the reaction is qualified, adding a 10% sodium carbonate aqueous solution to enable PH to range from 7 to 8, performing standing and layering, recovering sodium bromide from an aqueous phase, heating an organic phase until reflux, removing water, dropwise adding formamide after water removal while water removal, after addition of the formamide, continuously removing water, after removal, performing sampling detection, performing washing after the reaction is qualified, performing sewage removal treatment on the aqueous phase, removing the cyclohexane from the organic phase to obtain a crude difenoconazole product, and refining the product with methanol to obtain a finished difenoconazole product. A closed-loop production technology is adopted, production of isomers can be effectively avoided, and the product purity can be increased.
Description
Technical field
The present invention relates to a kind of preparation technology of difenoconazole technical material, belong to the synthesis technical field of pesticide original medicine.
Background technology
Difenoconazole, also known as Difenoconazole, is that in triazole bactericidal agent, security is higher.Be widely used in the crop such as fruit tree, vegetables, effectively prevent and treat black spot, anthrachose of grape, white rot, spot defoliation, Powdery Mildew, brown spot, rust, stripe rust, head blight etc.
Synthesis mainly 2-brooethyl-2-(the chloro-4-of 2-(4-chlorophenoxy) the phenyl)-4-methyl isophthalic acid of existing difenoconazole, 3-dioxolane and triazole sylvite react, and in the process of reaction, have isomer to generate, use closed loop method, the generation of isomery can be avoided.For this reason, a kind of new technical scheme is needed to solve above-mentioned technical problem.
Summary of the invention
The object of this invention is to provide a kind of brand-new technique to prepare difenoconazole, this preparation technology overcomes above-mentioned deficiency.
The technical solution used in the present invention is:
A kind of preparation technology of difenoconazole technical material, its reactions steps is specially: by 2-brooethyl-2-(the chloro-4-of 2-(4-chlorophenoxy) phenyl)-4-methyl isophthalic acid, 3-dioxolane, reactor put into by cyclohexane and normal-butyl brometo de amonio, control temperature 35-45 DEG C, drip hydrazine hydrate, drip 3-4 hour consuming time, be added dropwise to complete insulation 2-3 hour, sampling detects, react qualified after, add 10% aqueous sodium carbonate, make PH=7-8, stratification, aqueous phase reclaims Sodium Bromide, organic phase is warming up to backflow, remove water, after water is de-dry, drip methane amide, limit drips, dewater in limit, treat that methane amide dropwises, continue dehydration, until de-complete after, sampling detects, react qualified after, wash, the process of aqueous phase decontaminated water, organic phase removes cyclohexane, obtain difenoconazole crude product, use refining methanol again, obtain difenoconazole finished product.
Further, described 2-brooethyl-2-(the chloro-4-of 2-(4-chlorophenoxy) phenyl)-4-methyl isophthalic acid, the mol ratio of 3-dioxolane and hydrazine hydrate is 1:1.12.
Further, described 2-brooethyl-2-(the chloro-4-of 2-(4-chlorophenoxy) phenyl)-4-methyl isophthalic acid, the mol ratio of 3-dioxolane and methane amide is 1:1.05.
Further, described 2-brooethyl-2-(the chloro-4-of 2-(4-chlorophenoxy) phenyl)-4-methyl isophthalic acid, 3-dioxolane, cyclohexane are 0.5mmol:100ml:1g with the add-on ratio of normal-butyl brometo de amonio.
Advantage of the present invention is: adopt closed loop method production technique, effectively can avoid the generation of isomery, improve the purity of product.
Embodiment
Embodiment 1
In 1000ml four-hole bottle, add 500ml cyclohexane, 5g normal-butyl brometo de amonio and 104.5g (0.25mol) 2-brooethyl-2-(the chloro-4-of 2-(4-chlorophenoxy) phenyl)-4-methyl isophthalic acid, 3-dioxolane, be warming up to 40 ± 5 DEG C, drip 80% hydrazine hydrate 17.5g, about 3 hours, be incubated 2 hours, sampling, react qualified after, add 10% aqueous sodium carbonate, make PH=7-8, stratification, aqueous phase reclaims Sodium Bromide, organic phase is warming up to backflow, remove water, after water is de-dry, drip methane amide 11.7g, limit drips, dewater in limit, treat that methane amide dropwises, continue dehydration, until de-complete after, sampling detects, react qualified after, wash, the process of aqueous phase decontaminated water, organic phase removes cyclohexane, obtain Difenoconazole crude product, use refining methanol again, obtain Difenoconazole finished product.Difenoconazole product 90.70g, content 95.12%.Yield 85%.
Embodiment 2
In 1000ml four-hole bottle, add 500ml cyclohexane, 5g normal-butyl brometo de amonio and 104.5g (0.25mol) 2-brooethyl-2-(the chloro-4-of 2-(4-chlorophenoxy) phenyl)-4-methyl isophthalic acid, 3-dioxolane, be warming up to 40 ± 5 DEG C, drip 80% hydrazine hydrate 17.5g, about 3 hours, be incubated 2 hours, sampling, react qualified after, add 10% aqueous sodium carbonate, make PH=7-8, stratification, aqueous phase reclaims Sodium Bromide, organic phase is warming up to backflow, remove water, after water is de-dry, drip methane amide 11.7g, limit drips, dewater in limit, treat that methane amide dropwises, continue dehydration, until de-complete after, sampling detects, react qualified after, wash, the process of aqueous phase decontaminated water, organic phase removes cyclohexane, obtain Difenoconazole crude product, use refining methanol again, obtain Difenoconazole finished product.Difenoconazole product 93.77g, content 93.12%.Yield 86%.
Claims (3)
1. the preparation technology of a difenoconazole technical material, it is characterized in that: reactions steps is specially: by 2-brooethyl-2-(the chloro-4-of 2-(4-chlorophenoxy) phenyl)-4-methyl isophthalic acid, 3-dioxolane, reactor put into by cyclohexane and normal-butyl brometo de amonio, control temperature 35-45 DEG C, drip hydrazine hydrate, drip 3-4 hour consuming time, be added dropwise to complete insulation 2-3 hour, sampling detects, react qualified after, add 10% aqueous sodium carbonate, make PH=7-8, stratification, aqueous phase reclaims Sodium Bromide, organic phase is warming up to backflow, remove water, after water is de-dry, drip methane amide, limit drips, dewater in limit, treat that methane amide dropwises, continue dehydration, until de-complete after, sampling detects, react qualified after, wash, the process of aqueous phase decontaminated water, organic phase removes cyclohexane, obtain difenoconazole crude product, use refining methanol again, obtain difenoconazole finished product.
2. the preparation technology of a kind of difenoconazole technical material according to claim 1, it is characterized in that: described 2-brooethyl-2-(the chloro-4-of 2-(4-chlorophenoxy) phenyl)-4-methyl isophthalic acid, the mol ratio of 3-dioxolane and hydrazine hydrate is 1:1.12.
3. the preparation technology of a kind of difenoconazole technical material according to claim 1, it is characterized in that: described 2-brooethyl-2-(the chloro-4-of 2-(4-chlorophenoxy) phenyl)-4-methyl isophthalic acid, the mol ratio of 3-dioxolane and methane amide is 1:1.05.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510418498.8A CN105061406A (en) | 2015-07-17 | 2015-07-17 | Preparation technology of difenoconazole technical material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510418498.8A CN105061406A (en) | 2015-07-17 | 2015-07-17 | Preparation technology of difenoconazole technical material |
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| CN105061406A true CN105061406A (en) | 2015-11-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510418498.8A Pending CN105061406A (en) | 2015-07-17 | 2015-07-17 | Preparation technology of difenoconazole technical material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107306965A (en) * | 2017-06-05 | 2017-11-03 | 江苏耕耘化学有限公司 | The application of tetrahydrochysene phenylate azoles in disinfectant use in agriculture or microbicide compositions is prepared and preparation method thereof |
| CN109833916A (en) * | 2019-03-22 | 2019-06-04 | 江苏禾本生化有限公司 | A kind of composite catalyst and preparation method thereof for propiconazole cyclization reaction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4766253A (en) * | 1987-05-04 | 1988-08-23 | Ciba-Geigy Corporation | Process for preparing chlorinated diphenyl ethers |
| CN101190900A (en) * | 2006-11-28 | 2008-06-04 | 江苏丰登农药有限公司 | Preparation method of omega- (1H-1, 2, 4-triazole-1-yl) -arylethanone |
| CN101525332A (en) * | 2008-03-04 | 2009-09-09 | 北京绿色农华植保科技有限责任公司 | Method for preparing stable difenoconazole technical material |
| CN102775395A (en) * | 2012-07-12 | 2012-11-14 | 江苏七洲绿色化工股份有限公司 | Preparation method of propiconazole and propiconazole intermediate |
-
2015
- 2015-07-17 CN CN201510418498.8A patent/CN105061406A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4766253A (en) * | 1987-05-04 | 1988-08-23 | Ciba-Geigy Corporation | Process for preparing chlorinated diphenyl ethers |
| CN101190900A (en) * | 2006-11-28 | 2008-06-04 | 江苏丰登农药有限公司 | Preparation method of omega- (1H-1, 2, 4-triazole-1-yl) -arylethanone |
| CN101525332A (en) * | 2008-03-04 | 2009-09-09 | 北京绿色农华植保科技有限责任公司 | Method for preparing stable difenoconazole technical material |
| CN102775395A (en) * | 2012-07-12 | 2012-11-14 | 江苏七洲绿色化工股份有限公司 | Preparation method of propiconazole and propiconazole intermediate |
Non-Patent Citations (1)
| Title |
|---|
| 李宗英，等: "新型杀菌剂苯醚甲环唑合成研究", 《应用化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107306965A (en) * | 2017-06-05 | 2017-11-03 | 江苏耕耘化学有限公司 | The application of tetrahydrochysene phenylate azoles in disinfectant use in agriculture or microbicide compositions is prepared and preparation method thereof |
| CN109833916A (en) * | 2019-03-22 | 2019-06-04 | 江苏禾本生化有限公司 | A kind of composite catalyst and preparation method thereof for propiconazole cyclization reaction |
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Application publication date: 20151118 |