CN103724233A - Synthesis method of novaluron - Google Patents
Synthesis method of novaluron Download PDFInfo
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- CN103724233A CN103724233A CN201310561651.3A CN201310561651A CN103724233A CN 103724233 A CN103724233 A CN 103724233A CN 201310561651 A CN201310561651 A CN 201310561651A CN 103724233 A CN103724233 A CN 103724233A
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Abstract
The invention discloses a synthesis method of novaluron. P-nitrophenol is taken as a starting material, and hydrogen peroxide and hydrochloric acid chloro are used for preparing 2-chloro-4-nitrophenol; an inorganic base catalyst and perfluorinated vinyl methyl ether are used for addition reaction, 2-chloro-4-nitro-1-(1, 1, 2-trifluoro-2-(trifluoro methoxy) ethoxy) benzene is obtained, then nitro is reduced to obtain 3-chloro-4-(1, 1, 2-trifluoro-2-(trifluoro methoxy) ethoxy) aniline, and finally, 3-chloro-4-(1, 1, 2-trifluoro-2-(trifluoro methoxy) ethoxy) aniline reacts with 2, 6-difluorobenzoyl isocyanate to obtain novaluron. According to the method, raw materials are low in cost and easy to obtain, the operation is simple and convenient, the cost is low, the side reaction is few, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation as the organic compound of agricultural chemicals; be specifically related to a kind of fluorine uride (chloro-4-[1 of N-[[3-; the fluoro-2-of 1,2-tri-(trifluoromethoxy) oxyethyl group] phenyl] formamyl]-2, the two fluorobenzamides of 6-) synthetic method.
Background technology
Fluorine uride, has another name called Rimon, is a kind of high-efficient low toxicity insecticide important in process for preparation of benzoylurea compounds, mainly by suppressing the chitinous synthetic object that reaches kill pests.Chitin is a widely distributed ammonia polysaccharide, invertebrates, particularly in arthropods (insect, crustacean) body, contains in a large number, and relative less in mollusk, annelid and nematode.Chitin is the primary structure composition of the chitin-protein complexes such as insect cuticle and peritrophic membrane, the integration composition of while or fungi (except oomycetes) and some alga cells walls, but be not present in plant and vertebrates.Just because of this difference, chitin is counted as a safety and has the sterilant target compared with strong selectivity.Chitinous synthetic in the new epidermis forming process of acyl group ureas strongly inhibited insect, the havoc insect molting by affecting the basic chitin-protein structure of insect exoskeleton, result makes epidermis fragile and soft, finally causes insect dehydration and dead.Fluorine uride is process for preparation of benzoylurea compounds of new generation, controls lepidopteran, aleyrodid and the leaf worm of fruit, vegetables, cotton and corn.Due to its higher biological activity, and more friendly to people and animals, it is one of pesticide species of desirable update.The development and utilization of fluorine uride is conducive to the development of China's green agriculture.
What the synthetic method of fluorine uride was seen in report is to be published in < < He'nan University of Technology journal (natural science edition) > > 29 volumes the 1st phase 64-67 page of 2008, take p-NP as raw material, the chloro-4-nitrophenols of 2-generating after chloro adopts iron powder that nitroreduction is become to amino, obtain the chloro-PAP of 2-, carry out addition reaction with perfluorovinyl sulfide methyl ether again, the perfluor aniline obtaining and the reaction of 2,6-difluoro benzoyl isocyanate generate fluorine uride.The method mainly contains following drawback: 1. adopt iron powder to make reductive agent, the three wastes enormous amount producing in industrial production, is difficult to process, larger to environmental hazard; 2. in the chloro-PAP of 2-and the addition reaction of perfluorovinyl sulfide methyl ether, except phenolic hydroxyl group reaction, also have the amino side reaction occurring with perfluor raw material.Expensive because of perfluorovinyl sulfide methyl ether, the generation of side reaction herein has not only increased the content of impurity but also has increased the consumption of expensive perfluor raw material, has increased cost.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned weak point, and research and design purity is high, yield is high, the synthetic method of stay-in-grade fluorine uride.
The invention provides a kind of synthetic method of fluorine uride.
The inventive method is take p-NP as starting raw material, obtains the chloro-4-nitrophenols of 2-in hydrochloric acid and hydrogen peroxide through chlorination; The chloro-4-nitrophenols of 2-and perfluorovinyl sulfide methyl ether generation addition reaction, make the chloro-4-nitro-1-of 2-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene; Through the hydrazine hydrate reduction of metal catalytic, obtain the chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline again; Further obtain fluorine uride with 2,6-difluoro benzoyl isocyanate generation condensation reaction.
The inventive method comprises the steps:
(1) chloro: take p-NP as starting raw material, prepare the chloro-4-nitrophenols of 2-with hydrogen peroxide and hydrochloric acid chloro.Particularly, p-NP is dissolved in hydrochloric acid, in 35～40 ℃ of dropping hydrogen peroxide, reaction 3-4 hour, obtains the chloro-4-nitrophenols of 2-after filtration.
(2) addition: adopt mineral alkali catalysis and perfluorovinyl sulfide methyl ether generation addition reaction, obtain the chloro-4-nitro-1-of 2-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene.Particularly, chloro-2-4-nitrophenols is dissolved in the mixed system of benzene kind solvent and polar solvent, under the catalysis of mineral alkali, reacts with perfluorovinyl sulfide methyl ether, obtain the chloro-4-nitro-1-(1 of 2-, the fluoro-2-of 1,2-tri-(trifluoromethoxy) oxyethyl group) benzene.
(3) reduction: obtain the chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline with hydrazine hydrate reduction nitro afterwards.Particularly, the chloro-4-nitro-1-(1,1 of 2-, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) benzene uses hydrazine hydrate for reductive agent under metal catalytic, obtain the chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline.
(4) condensation: last with 2,6-difluoro benzoyl isocyanate carries out condensation reaction and obtains fluorine uride.Particularly, by chloro-3-4-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline and the reaction of 2,6-difluoro benzoyl isocyanate, filter afterwards, be dried and can obtain fluorine uride.
In the synthetic route of having reported, be that chloro-2-4-nitrophenols is first used to metallic reducing agent, as iron powder, zinc powder etc., by nitroreduction, be amino, and then carry out addition reaction with perfluorovinyl sulfide methyl ether.In the method, the metal catalyst using on the one hand, the three wastes enormous amount producing in industrial production, and be difficult to process, the harm that environment is produced is larger; On the other hand, chloro-2-4-nitrophenols is reduced to after the chloro-PAP of 2-, then while reacting with perfluorovinyl sulfide methyl ether, except the phenolic hydroxyl group of normal generation and reacting of perfluor raw material, also has and aminoly occur with the side reaction of perfluor raw material.So, this step reaction not only can produce impurity, and has strengthened the consumption of perfluor raw material.Because perfluor raw material is the most expensive raw material in whole route, the unit consumption increase of this raw material will certainly cause the increase of whole raw materials cost.
The present invention improves the synthesis technique of fluorine uride, and chloro-2-4-nitrophenols is first reacted with perfluorovinyl sulfide methyl ether, has avoided the generation of side reaction; Ensuing reduction reaction is used hydrazine hydrate as reductive agent, has avoided the use of metallic reducing agent, greatly reduces three wastes generation, is beneficial to industrial production and environment protection.
The solvent of the chloro-4-nitrophenols of step of the present invention (2) 2-and the addition of perfluorovinyl sulfide methyl ether is the mixed system of benzene kind solvent and polar solvent, and benzene kind solvent is selected from benzene, toluene or dimethylbenzene; Polar solvent is selected from methyl-sulphoxide, acetonitrile, dioxane, DMF, N-Methyl pyrrolidone or N,N-dimethylacetamide, and the mixed volume per-cent of benzene kind solvent and polar solvent is 0.1:1～4:1, is preferably 1:1～2.3:1.
The chloro-4-nitrophenols of 2-and the solvent load of perfluorovinyl sulfide methyl ether addition reaction and the weight ratio of substrate are 2.0～40:1, are preferably 5.0～30:1.
The mineral alkali of the chloro-4-nitrophenols of 2-and the addition reaction of perfluorovinyl sulfide methyl ether is sodium hydroxide, potassium hydroxide, hydrated barta, salt of wormwood, sodium carbonate or cesium carbonate.Mol ratio 0.05～the 0.8:1 of the chloro-4-nitrophenols of the consumption of mineral alkali and 2-, is preferably 0.1～0.6:1.
The temperature of reaction of the chloro-4-nitrophenols of 2-and the addition reaction of perfluorovinyl sulfide methyl ether is-50～50 ℃, is preferably-10～10 ℃; Reaction times is 0.5～24 hour, is preferably 5～10 hours.
The solvent of the reduction reaction of the chloro-4-nitro-1-of step of the present invention (3) 2-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene is selected from methyl alcohol, ethanol, Virahol, the trimethyl carbinol or isopropylcarbinol; The weight ratio of reaction solvent consumption and substrate is 2.0～30:1, is preferably 5.0～10.0:1; Temperature of reaction is the boiling point that room temperature arrives solvent for use.
The metal catalyst that reduction reaction is used is selected from Raney's nickel, palladium-carbon catalyst, palladium chloride, tetrakis triphenylphosphine palladium, iron trichloride or [two (diphenylphosphine) ferrocene of 1,1-] palladium chloride; The weight ratio of catalyst levels and substrate is 0.001～0.3:1.
The hydrazine hydrate that the reductive agent that reduction reaction is used is 85%; The weight ratio of hydrazine hydrate consumption and substrate is 1.0～10:1, preferably 2.0～5.0:1.
The chloro-4-(1 of step of the present invention (4) 3-, 1, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) solvent of condensation reaction of aniline and 2,6-difluoro benzoyl isocyanate is selected from methylene dichloride, 1,2-ethylene dichloride, chlorobenzene or dichlorobenzene; The weight ratio of the chloro-4-of solvent load and 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline is 2.0～30:1, preferably 5.0～20:1.
The temperature of reaction of condensation reaction is-10～20 ℃; Reaction times is 1～10 hour.
The inventive method advantage: 1, the chloro-4-nitrophenols of 2-and perfluorovinyl sulfide methyl ether generation addition reaction, avoided the generation of side reaction, reduce the generation of impurity in producing, also reduced the consumption of expensive raw material perfluorovinyl sulfide methyl ether simultaneously, reduced cost; 2, the chloro-4-nitro-1-(1 of 2-, the fluoro-2-of 1,2-tri-(trifluoromethoxy) oxyethyl group) hydrazine hydrate reduction of metal catalytic that the reduction reaction of benzene adopts, avoided use metallic reducing agent, greatly reduce the generation of the three wastes, environmental friendliness; 3, respectively walk safety simple to operate, convenient post-treatment, equipment requirements is low, is applicable to industrialized production.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but and unrestricted range of application of the present invention.
Embodiment 1: the chloro-4-nitrophenols of preparation 2-:
In 500ml flask, add 35 grams of p-NPs, 205 grams of concentrated hydrochloric acids, stir lower 26 grams, the hydrogen peroxide that drips, control temperature below 30 ℃, react after 3 hours, filter, filter cake washes with water to neutrality, after dry, use ethylene dichloride recrystallization, obtain 35g yellow solid, productive rate 80%.
Embodiment 2: the preparation chloro-4-nitro-1-of 2-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene:
In 250ml flask, add 3.48 grams of the chloro-4-nitrophenolss of 2-, toluene 40mL, 0.37 gram, methyl-sulphoxide 40mL and potassium hydroxide, stir borehole cooling to 5 ℃, passes into 3.32 grams of perfluorovinyl sulfide methyl ethers, after ventilation finishes, be incubated 0-10 ℃ of reaction 10 hours, add 50mL water, layering, water extracts once with 20mL toluene, merges organic phase, anhydrous sodium sulfate drying, filters, concentrated, obtain 5.86 grams of yellowish brown solids, productive rate 86%.
1HNMR(400MHz，CDCl
3)：δ5.97(dt，J=56.0，4.0Hz，1H)，7.48(d，J=9.2Hz，1H)，8.13(dd，J=2.8，9.2Hz，1H)，8.32(d，J=2.8Hz，1H)；
19FNMRδppm-144.84，-86.40，-59.75。
Embodiment 3: the preparation chloro-4-nitro-1-of 2-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene:
In 100ml flask, add 6.96 grams of the chloro-4-nitrophenolss of 2-, dimethylbenzene 20mL, 1 gram, methyl-sulphoxide 20mL and potassium hydroxide, stir borehole cooling to 5 ℃, passes into 6.64 grams of perfluorovinyl sulfide methyl ethers, after ventilation finishes, be incubated 0-10 ℃ of reaction 10 hours, add 100mL water, layering, water extracts once with 50mL toluene, merges organic phase, anhydrous sodium sulfate drying, filters, concentrated, obtain 10.38 grams of yellowish brown solids, productive rate 76.2%.
Embodiment 4: the preparation chloro-4-nitro-1-of 2-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene:
In 100ml flask, add 8.71 grams of the chloro-4-nitrophenolss of 2-, toluene 33mL, 1.5 grams, DMF 15mL and potassium hydroxide, stir borehole cooling to 5 ℃, pass into 5.0 grams of perfluorovinyl sulfide methyl ethers, after ventilation finishes, be incubated 0-10 ℃ of reaction 10 hours, add 100mL water, layering, water extracts once with 50mL toluene, merge organic phase, anhydrous sodium sulfate drying, filters, concentrated, obtain 15.2 grams of yellowish brown solids, productive rate 89%.
Embodiment 5: the preparation chloro-4-nitro-1-of 2-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene:
In 100ml flask, add 3.48 grams of the chloro-4-nitrophenolss of 2-, toluene 36mL, 1.06 grams, acetonitrile 18mL and sodium carbonate, stir borehole cooling to 5 ℃, passes into 3.32 grams of perfluorovinyl sulfide methyl ethers, after ventilation finishes, intensification 40-45 ℃ is reacted 10 hours, adds 100mL water, layering, water extracts once with 50mL toluene, merges organic phase, anhydrous sodium sulfate drying, filters, concentrated, obtain 4.17 grams of yellowish brown solids, productive rate 61.4%.
Embodiment 6: the preparation chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline
In 100mL flask, add the chloro-4-nitro-1-(1,1 of 2-, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) benzene 6.79g, ethanol 48mL and iron trichloride 105mg, reflux, drip hydrazine hydrate 16.5mL, dropwise rear back flow reaction 24 hours, filtered while hot, filter cake washing with alcohol, filtrate is concentrated, filtration obtains brown solid, and vacuum-drying obtains 5.14g, productive rate 83%.
1HNMR(400MHz，CDCl
3)：δ3.75(bs，2H)，5.96(dt，J=54.4，3.2Hz，1H)，6.52(dd，J=2.8，8.8Hz，1H)，6.73(d，J=2.8Hz，1H)，7.08(d，J=8.8Hz，1H)。
Embodiment 7: the preparation chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline
In 250mL flask, add the chloro-4-nitro-1-(1,1 of 2-, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) benzene 17g, methyl alcohol 90mL and palladium chloride 170mg, reflux, drip hydrazine hydrate 49.4mL, dropwise rear back flow reaction 24 hours, filtered while hot, filter cake methanol wash, filtrate is concentrated, filtration obtains brown solid, and vacuum-drying obtains 13.3g, productive rate 85.8%.
Embodiment 8: prepare fluorine uride
In 100mL flask, add the chloro-4-(1,1 of 3-, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) aniline 6.19g and ethylene dichloride 60mL, be cooled to-5 ℃, drip 2,6-difluoro benzoyl isocyanate 4g, after dropwising, rises to 10 ℃, react 10 hours, filter, solid ethylene dichloride recrystallization, dry, obtain off-white color solid 8.38g, productive rate 85%.
Embodiment 9: prepare fluorine uride
In 100mL flask, add the chloro-4-(1,1 of 3-, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) aniline 7.43g and orthodichlorobenzene 75mL, be cooled to-5 ℃, drip 2,6-difluoro benzoyl isocyanate 5g, after dropwising, rises to 10 ℃, react 10 hours, filter, solid ethylene dichloride recrystallization, dry, obtain off-white color solid 8.02g, productive rate 67.8%.
Claims (10)
1. a synthetic method for fluorine uride, it comprises the following steps:
(1) chloro: take p-NP as starting raw material, prepare the chloro-4-nitrophenols of 2-with hydrogen peroxide and hydrochloric acid chloro;
(2) addition: adopt mineral alkali catalysis and perfluorovinyl sulfide methyl ether generation addition reaction, obtain the chloro-4-nitro-1-of 2-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene;
(3) reduction: obtain the chloro-4-of 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline with hydrazine hydrate reduction nitro afterwards;
(4) condensation: last with 2,6-difluoro benzoyl isocyanate carries out condensation reaction and obtains fluorine uride.
2. according to the synthetic method of claim 1, it is characterized in that each step is specially:
(1) chloro: p-NP is dissolved in hydrochloric acid, and in 35～40 ℃ of dropping hydrogen peroxide, reaction 3-4 hour, obtains the chloro-4-nitrophenols of 2-after filtration;
(2) addition: chloro-2-4-nitrophenols is dissolved in the mixed system of benzene kind solvent and polar solvent, under the catalysis of mineral alkali, react with perfluorovinyl sulfide methyl ether, obtain the chloro-4-nitro-1-of 2-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene;
(3) reduction: the chloro-4-nitro-1-(1 of 2-, 1, the fluoro-2-of 2-tri-(trifluoromethoxy) oxyethyl group) benzene uses hydrazine hydrate for reductive agent under the catalysis of metal catalyst, obtain the chloro-4-(1 of 3-, the fluoro-2-of 1,2-tri-(trifluoromethoxy) oxyethyl group) aniline;
(4) condensation: by chloro-3-4-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline and the reaction of 2,6-difluoro benzoyl isocyanate, filter afterwards, be dried and can obtain fluorine uride.
3. according to the synthetic method of claim 1-2, it is characterized in that the mineral alkali in described step (2) is selected from sodium hydroxide, potassium hydroxide, hydrated barta, salt of wormwood, sodium carbonate or cesium carbonate.
4. according to the synthetic method of claim 1-2, it is characterized in that the mixed system of described step (2) use benzene kind solvent and polar solvent, benzene kind solvent is selected from benzene, toluene or dimethylbenzene; Polar solvent is selected from methyl-sulphoxide, acetonitrile, dioxane, DMF, N-Methyl pyrrolidone or N,N-dimethylacetamide, and the mixed volume per-cent of benzene kind solvent and polar solvent is 0.1:1～4:1, is preferably 1:1～2.3:1.
5. according to the synthetic method of claim 1-4 any one, it is characterized in that, in described step (2), the mol ratio of the chloro-4-nitrophenols of the consumption of inorganic base catalyst and 2-is 0.05～0.8:1, is preferably 0.1～0.6:1.
6. according to the synthetic method of claim 1-5 any one, it is characterized in that the weight ratio of the middle solvent load of described step (2) and the chloro-4-nitrophenols of 2-is 2.0～40:1; Be preferably 5.0～30:1.
7. according to the synthetic method of claim 1-6 any one, it is characterized in that the temperature of reaction of described step (2) is-50～50 ℃, be preferably-10～10 ℃; Time is 0.5～24 hour, is preferably 5～10 hours.
8. according to the synthetic method of claim 1-7 any one, it is characterized in that described step (3) carries out under metal catalyst catalysis, metal catalyst is wherein selected from Raney's nickel, palladium-carbon catalyst, palladium chloride, tetrakis triphenylphosphine palladium, iron trichloride or [two (diphenylphosphine) ferrocene of 1,1-] palladium chloride; Solvent is methyl alcohol, ethanol, Virahol, isopropylcarbinol or the trimethyl carbinol; The temperature of reaction by room temperature to the boiling point of use solvent.
9. according to the synthetic method of claim 1-8 any one, it is characterized in that consumption and the chloro-4-nitro-1-(1 of 2-of the metal catalyst in described step (3), the fluoro-2-of 1,2-tri-(trifluoromethoxy) oxyethyl group) weight ratio of benzene is 0.001～0.3:1; The weight ratio of the chloro-4-nitro-1-of the consumption of hydrazine hydrate and 2-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene is 1.0～10:1, is preferably 2.0～5.0:1; The weight ratio of the chloro-4-nitro-1-of solvent load and 2-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) benzene is 2.0～30:1; Be preferably 5.0～10:1.
10. according to the synthetic method of claim 1-9 any one, it is characterized in that the solvent of described step (4) condensation is selected from methylene dichloride, 1,2-ethylene dichloride, chlorobenzene or dichlorobenzene; The weight ratio of the chloro-4-of solvent load and 3-(the fluoro-2-of 1,1,2-tri-(trifluoromethoxy) oxyethyl group) aniline is 2.0～30:1, preferably 5.0～20:1; The temperature of reaction of described step (4) is-10～20 ℃; 1～10 hour reaction times.
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| CN110746322A (en) * | 2019-10-16 | 2020-02-04 | 江苏艾科姆检测有限公司 | N- [ 3-chloro-4- (1,1, 2-trifluoro-2-trifluoromethoxy-ethyl) -phenyl ] -2, 6-difluoro-benzamidine, preparation method and application |
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| CN110746322A (en) * | 2019-10-16 | 2020-02-04 | 江苏艾科姆检测有限公司 | N- [ 3-chloro-4- (1,1, 2-trifluoro-2-trifluoromethoxy-ethyl) -phenyl ] -2, 6-difluoro-benzamidine, preparation method and application |
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