CN1065859C - Process for preparing phenoxyether as intermediate of agricultural chemicals - Google Patents
Process for preparing phenoxyether as intermediate of agricultural chemicals Download PDFInfo
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- CN1065859C CN1065859C CN98117806A CN98117806A CN1065859C CN 1065859 C CN1065859 C CN 1065859C CN 98117806 A CN98117806 A CN 98117806A CN 98117806 A CN98117806 A CN 98117806A CN 1065859 C CN1065859 C CN 1065859C
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- reaction
- trichlorophenoxy
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- ethyl chloride
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Abstract
The present invention relates to a method for preparing N-n-propyl-N-2-(2, 4, 6-trichlorophenoxyl)-ethylamine. The method comprises the following steps: making 2, 4, 6-trichlorophenol react with 1, 2-dichloroethane under the existence of potassium hydroxide, and then making the obtained product react with 2-(2, 4, 6-trichlorophenoxyl)-ethylchlorine and propylamine.
Description
The present invention relates to the method and the application in producing the sterilant prochloraz thereof of N-n-propyl-N-2-(2,4, the 6-Trichlorophenoxy)-ethamine of preparation formula I.
Formula I compound is the intermediate as preparation sterilization prochloraz.
The method of several preparation I compounds is disclosed in the prior art.
For example, US3,991,071 have described a kind ofly with 2,4, and 6-Trichlorophenol and glycol dibromide are the method for starting raw material preparation I compound.This method is in the presence of alkali such as sodium hydroxide, makes 2,4, and 6-Trichlorophenol and glycol dibromide carry out the dehydrobromination reaction, and will generate 2,4, and 6-Trichlorophenoxy monobromoethane and Tri N-Propyl Amine reaction provide formula I compound.The shortcoming of this method is, the costing an arm and a leg of ethylene dibromide, and toxicity is big and be carcinogenic substance.
It is the method for starting raw material preparation I compound with 2-phenoxy group-ethanol that EP404092 has described a kind of.This method is by using chlorine in the presence of HCl or urea, optionally chlorination 2-phenoxy group-ethanol forms 2-(2,4, the 6-Trichlorophenoxy)-ethanol, and this 2-(2,4, the 6-Trichlorophenoxy)-ethanol and thionyl chloride reacted in the presence of catalyzer, reaction product 2-(2,4,6-three phenoxy bases)-ethyl chloride is followed and Tri N-Propyl Amine reacts, and provides Compound I.
It is the method for starting raw material preparation I compound with 2-phenoxy group-ethanol that EP403929 has also described a kind of.This method is in the presence of catalyzer, handles 2-phenoxy group-ethanol with thionyl chloride, then with the 2-phenoxy group-ethyl chloride chlorine gas selecting ground chlorination that forms, reaction product 2-(2,4, the 6-Trichlorophenoxy)-ethyl chloride is followed and Tri N-Propyl Amine reacts, and provides Compound I.
The inventive method is compared with the method among EP404923, the EP404092, and advantage is that a) step is few, and reaction process is short; 2) reduce by product, help improving the content of product; 3) do not use chlorine, improved security.
The method that the purpose of this invention is to provide a kind of improved preparation I compound newly.Another object of the present invention provides the method that is easy to industrialization and prepares prochloraz with high yield.
Surprising is that above-mentioned purpose of the present invention can realize by the preparation method who comprises following steps:
A. for example in the presence of the potassium hydroxide, make 2,4 at alkali, 6-Trichlorophenol and 1, the reaction of 2-ethylene dichloride forms 2-(2,4, the 6-Trichlorophenoxy)-ethyl chloride;
B. make the direct and Tri N-Propyl Amine reaction of 2-(2,4, the 6-Trichlorophenoxy)-ethyl chloride, provide formula I compound.
Reaction method of the present invention can be described with following reaction scheme usually:
When carrying out the inventive method step a, with respect to every mole 2,4, the 6-Trichlorophenol can adopt the 2-8 mole, the ethylene dichloride of preferred 4-6 mole.
The inventive method step a is that for example potassium hydroxide, sodium hydroxide, especially potassium hydroxide carry out under existing at alkali.Can adopt the alkali of equimolar amount, but excessive a little, for example with respect to every mole 2,4, it can be favourable to reaction that the 6-Trichlorophenol adopts the alkali of 1.0-1.5 mole.
The temperature of reaction of step a is 80-130 ℃, and reaction pressure is a 2-4 normal atmosphere, and the reaction times is 4-8 hour.
When carrying out the inventive method step b, with respect to every mole of 2-(2,4, the 6-Trichlorophenoxy)-ethyl chloride, can adopt the 1-6 mole, the Tri N-Propyl Amine of preferred 2-4 mole.
The temperature of reaction of step b is 70-110 ℃ a temperature, and reaction pressure is 1 to 3 normal atmosphere, and the reaction times is 4-8 hour.
End product amine is (referring to for example EP0403952) or prepare the mode that provides among the embodiment by the present invention and separate by known methods.
Therefore, the inventive method provides the method that is easy to industrialization and prepares 2-(2,4, the 6-Trichlorophenoxy)-ethyl chloride and formula I compound with high yield.In addition, according to US3,991,071, formula I compound can with phosgene reaction, with imidazoles reaction, provide prochloraz subsequently.
Though the present invention provides embodiment hereinafter and is described in further detail, should be appreciated that the present invention is not limited to these embodiment.
Embodiment 1
The preparation of 2-(2,4, the 6-Trichlorophenoxy)-ethyl chloride
In 3000 liters of stainless steel cauldrons, add successively 500 kilograms 2,4, the potassium hydroxide aqueous solution of 6-Trichlorophenol, 750 kilograms of ethylene dichloride and 556 kilogram 25% after the stirring and dissolving, seals with N2, slow heated and stirred, control reaction temperature is at 90-100 ℃, and reaction pressure is 3 normal atmosphere, reacts 4 hours, reaction finishes, be cooled to about 40 ℃, pressure drops to normal pressure, and layer oily matter is put into another 2000 liters of reactors.Ethylene dichloride is taken off in distillation, gets 665.3kg (90% content) title compound.
Embodiment 2
The preparation of 2-(2,4, the 6-Trichlorophenoxy)-ethyl chloride
In 3000 liters of stainless steel cauldrons, add successively 500 kilograms 2,4, the potassium hydroxide aqueous solution of 6-Trichlorophenol, 1000 kilograms of ethylene dichloride and 1100 kilogram 25%, after the stirring and dissolving,, be warming up to about 130 ℃ with the N2 sealing, reaction pressure is 4 normal atmosphere, reacted 6 hours, reaction finishes, and is cooled to about 40 ℃, pressure drops to normal pressure, and layer oily matter is put into another 2000 liters of reactors.Ethylene dichloride is taken off in distillation, gets 649 kilograms of (91.5% content) title compounds.
Embodiment 3
In 3000 liters stainless steel cauldron, add the Tri N-Propyl Amine of 600 kilograms of 2-(2,4, the 6-Trichlorophenoxy)-ethyl chloride and 820 kilograms, with the air of nitrogen replacement top, good seal.Heat temperature raising is to about 100 ℃, and pressure rises to 4 normal atmosphere, reacts 8 hours.Add about 50 kg of hydrogen sodium oxides, boil off excessive Tri N-Propyl Amine, divide water-yielding stratum, obtain the title compound of 460 kilograms (foldings hundred).
Claims (3)
1. method for preparing N-n-propyl-N-2-(2,4, the 6-Trichlorophenoxy)-ethamine.
It is characterized in that described method comprises following steps:
A. in the presence of alkali, make 2,4,6-Trichlorophenol and 1, the reaction of 2-ethylene dichloride forms 2-(2,4, the 6-Trichlorophenoxy)-ethyl chloride;
B. make the direct and Tri N-Propyl Amine reaction of 2-(2,4, the 6-Trichlorophenoxy)-ethyl chloride, form N-n-propyl-N-2-(2,4, the 6-Trichlorophenoxy)-ethamine.
2. according to the method for claim 1, it is characterized in that alkali used among the step a is potassium hydroxide.
3. according to the method for claim 1 or 2, the temperature of reaction that it is characterized in that step a is 80-130 ℃, and reaction pressure is a 2-4 normal atmosphere; The temperature of reaction of step b is 70-110 ℃, and reaction pressure is a 1-3 normal atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117806A CN1065859C (en) | 1998-08-27 | 1998-08-27 | Process for preparing phenoxyether as intermediate of agricultural chemicals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117806A CN1065859C (en) | 1998-08-27 | 1998-08-27 | Process for preparing phenoxyether as intermediate of agricultural chemicals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1246473A CN1246473A (en) | 2000-03-08 |
| CN1065859C true CN1065859C (en) | 2001-05-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98117806A Ceased CN1065859C (en) | 1998-08-27 | 1998-08-27 | Process for preparing phenoxyether as intermediate of agricultural chemicals |
Country Status (1)
| Country | Link |
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| CN (1) | CN1065859C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402608B (en) * | 2008-11-25 | 2011-11-02 | 乐斯化学有限公司 | Method for producing bactericide prochloraz |
| CN109651177A (en) * | 2018-12-20 | 2019-04-19 | 江西省隆南药化有限公司 | A kind of preparation method of benzethonium chloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033626A (en) * | 1987-06-25 | 1989-07-05 | 国际壳牌研究有限公司 | Thiazole derivative |
| JPH0565252A (en) * | 1991-06-25 | 1993-03-19 | Mitsubishi Gas Chem Co Inc | Phenoxyethylamine and agricultural and horticultural fungicide |
| IES64136B2 (en) * | 1994-01-19 | 1995-07-12 | Vandros Limited | Process for manufacturing imidazole derivatives |
-
1998
- 1998-08-27 CN CN98117806A patent/CN1065859C/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033626A (en) * | 1987-06-25 | 1989-07-05 | 国际壳牌研究有限公司 | Thiazole derivative |
| JPH0565252A (en) * | 1991-06-25 | 1993-03-19 | Mitsubishi Gas Chem Co Inc | Phenoxyethylamine and agricultural and horticultural fungicide |
| IES64136B2 (en) * | 1994-01-19 | 1995-07-12 | Vandros Limited | Process for manufacturing imidazole derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1246473A (en) | 2000-03-08 |
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Decision date of declaring invalidation: 20180821 Decision number of declaring invalidation: 36953 Granted publication date: 20010516 |