CN1010942B - Synthetic process for fluoro-cyano chrysanthemate - Google Patents
Synthetic process for fluoro-cyano chrysanthemateInfo
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- CN1010942B CN1010942B CN 88105866 CN88105866A CN1010942B CN 1010942 B CN1010942 B CN 1010942B CN 88105866 CN88105866 CN 88105866 CN 88105866 A CN88105866 A CN 88105866A CN 1010942 B CN1010942 B CN 1010942B
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- phenyl
- acid
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- difluoro
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Abstract
The present invention relates to a synthetic process for fluoro-cyano chrysanthemate. 2-(4-chloro-phenyl)-3-methyl butanoic acid is used as a raw material to prepare the fluoro-cyano chrysanthemate by four-step reactions, such as hydrolysis, difluoro-methyl etherification, acyl-chlorination and condensation. Compared with the existing method, the synthetic process reduces the reaction steps by half, shortens the reaction time and greatly improves the total yield.
Description
The present invention relates to the improvement of fluoro-Cyano chrysanthemate synthetic method.
Fluoro-Cyano chrysanthemate (Flucythrinatc) is the fluorine-containing pyrethroid insecticides of the eighties exploitation, have characteristics such as wide spectrum, efficient, low residue, and have better light, thermostability than other quasi-chrysanthemum ester, be suitable for high temperature, high light weather control cotton pest in the cotton growth process, also be used for vegetables, pest control on fruit tree and other land for growing field crops farm crop also can be mixed with mixed preparation respectively with Multiple Pesticides in addition, demonstrate wide spectrum, efficient, special efficacy and distinguishing feature such as quick-acting.
The synthetic method of fluoro-Cyano chrysanthemate, generally adopt with the aubepine is raw material, form (referring to United States Patent (USP) 4 through eight steps reaction such as reduction, chloro, cyano group replacement, isopropylation, hydrolysis, difluoro ether, chloride and condensation, 199,595 and 4,239,777, the Chemical Industry and Engineering Society of China Pesticide Science is the nd Annual Meeting collection for the third time), this synthetic method reaction formula is:
This synthetic method, reactions steps is many, the time is long, total recovery has only 20～25%(in aubepine), it is that solvent can not reclaim that dioxane is adopted in the difluoro ether reaction, hydrolysis reaction need exhaust a large amount of Hydrogen bromides, serious three wastes in addition.The present invention adopts four step synthesis methods, has not yet to see report.
The synthetic method that the purpose of this invention is to provide the fluoro-Cyano chrysanthemate that a kind of reactions steps is few, the reaction times is short, total recovery is high.
The objective of the invention is to realize by four-step reactions such as following hydrolysis, difluoro ether, chloride and condensations:
1. hydrolysis reaction:
In autoclave, add the 2-(4-chloro-phenyl-)-3 Methylbutanoic acid, the aqueous sodium hydroxide solution of concentration 10～30% and copper 8-quinolinolate, its mol ratio is 1: 4～8: 0.08～0.12.Under 120～180 ℃ of conditions, stir 8～15 hours (pressure is generally 4.5～6 kilograms in the still), cooling back elimination catalyzer, separate out white precipitate after the filtrate acidifying, filter after scouring and oven dry, get the 2-(4-hydroxy phenyl)-the 3 Methylbutanoic acid white powder, its fusing point is 166～167 ℃, its purity of gas chromatographic analysis＞95%, pure yield 85～95%.
2. difluoro ether reaction
Agitator is being housed, prolong, add the 2-(4-hydroxy phenyl in the reaction flask of thermometer and airway)-3 Methylbutanoic acid, sodium hydroxide, triethyl benzyl ammonia chloride, its mol ratio is 1: 5～10: 0.05～0.10, add sherwood oil (2000～6000 milliliters of/mole butyric acid) and water (200～600 milliliters of/mole butyric acid) again, be warming up to 40～80 ℃ and feed fluorine Lyons-22(1-4 moles/mole butyric acid again), with the reaction mixture dilute with water, water layer with petroleum ether after the concentrated hydrochloric acid acidifying is used the vinyl acetic monomer extracting 3 times again, merge organic layer, water washing, the anhydrous magnesium sulfate drying after-filtration, boil off solvent, get faint yellow solid, use 1: 0.6～1 methylene dichloride and normal hexane mixed solvent recrystallization again, the elimination white precipitate, be unreacted 2-(4-hydroxy phenyl)-3 Methylbutanoic acid, but recirculation is used.The filtrate evaporate to dryness gets 2-(4-difluoro-methoxy phenyl)-the 3 Methylbutanoic acid yellow solid, its fusing point is 60～61 ℃, its purity of gas chromatographic analysis＞90%; Pure yield 40～50%.
3. acyl chloride reaction
The adding mol ratio is 1: 0.4～0.7 2-(4-difluoro-methoxy phenyl in the reactor that prolong and calcium chloride tube are housed)-3 Methylbutanoic acid and phosphorus trichloride, be warming up to 60～100 ℃ of reactions 1～3 hour, remove the phosphorous acid of remaining phosphorus trichloride and generation, get 2-(4-difluoro-methoxy phenyl)-the light yellow transparent liquid of 3-methylbutyryl chlorine.This liquid is through its purity of gas chromatographic analysis＞80%, pure yield 82～92%.
4. condensation reaction
In the reactor of whipping appts is housed, add 2-(4-difluoro-methoxy phenyl by 1: 1: 0.05～0.10 mol ratio)-3-methylbutyryl chlorine, 3-phenoxy benzaldehyde and triethyl benzyl ammonia chloride after, add toluene (500～2000 milliliters of/mole acyl chlorides) again, temperature control drips sodium cyanide solution (1～3 moles/mole acyl chlorides) between 5～25 ℃, continue to be stirred to react completely (detecting with thin-layer chromatography).Tell organic layer, water layer is incorporated organic layer into behind the methylbenzene extraction 3 times, with 5% hydrochloric acid, water and saturated common salt water washing, anhydrous magnesium sulfate drying, get thick product after boiling off solvent, again through silica gel column chromatography (sorbent material: silica gel H, 10～40 μ, eluent: vinyl acetic monomer-normal hexane) get purity (high pressure liquid chromatographic analysis)＞95%, the fluoro-Cyano chrysanthemate elaboration of pure yield 85～95%.
Reaction formula of the present invention is:
Compare with existing synthetic method, the present invention only contains four-step reaction, makes reactions steps reduce half, and the reaction times shortens, and total recovery is brought up to 60～65%(in the 2-(4-chloro-phenyl-)-3 Methylbutanoic acid).In addition, the present invention does not comprise the isopropylation that reaches 4 days consuming time in the existing method, and has avoided using expensive dioxane and concentrated hydrobromic acid.
Embodiment:
1. hydrolysis reaction
The 2-(4-chloro-phenyl-)-and 3 Methylbutanoic acid 0.04mol, 13%NaOH solution 65ml, copper 8-quinolinolate 0.004mol, 150 ℃ were reacted 10 hours, got 6.95 gram products, purity 96%, pure yield 91.5%.
2. difluoro ether reaction
The 2-(4-hydroxy phenyl)-and 3 Methylbutanoic acid 0.1mol, the 40mlNaOH aqueous solution (NaOH:1mol), sherwood oil 400ml, triethyl benzyl ammonia chloride 0.01mol, fluorine Lyons-22 0.2mol, 65 ℃ of temperature of reaction.Product purity 92%, pure yield 46%.
3. acyl chloride reaction
(RS)-2-(4-difluoro-methoxy phenyl)-3 Methylbutanoic acid 0.07mol, PCl
30.047mol 85 ℃ were reacted 2 hours.Product purity 82%, pure yield 88.8%.
4. condensation reaction
2-(4-difluoro-methoxy phenyl)-and 3-methylbutyryl chlorine 0.062mol, 3-phenoxy benzaldehyde 0.062mol, triethyl benzyl ammonia chloride 1.1 grams, sodium cyanide 0.074mol(is dissolved in 16 ml waters), toluene 64ml, 15 ℃ of temperature of reaction.Through column chromatography product purity 97.75%, pure yield 88.97%.
Claims (1)
1, a kind of synthetic method of fluoro-Cyano chrysanthemate is characterized in that forming through the following steps reaction:
(1) in autoclave, adds 2-(4-chloro-phenyl-)-3 Methylbutanoic acid, concentration is 10～30% aqueous sodium hydroxide solution and copper 8-quinolinolate, its mol ratio is 1: 4～8: 0.08～0.12, under 120～180 ℃ of conditions, stirred 8～15 hours, cooling back elimination oxine copper catalyst, filtrate through hcl acidifying more after filtration, washing and oven dry, 2-(4-the hydroxy phenyl)-3 Methylbutanoic acid of white powder;
(2) agitator is being housed, prolong, add 2-(4-hydroxy phenyl)-3 Methylbutanoic acid in the reaction flask of thermometer and airway, sodium hydroxide, triethyl benzyl ammonia chloride, its mol ratio is 1: 5～10: 0.05～0.10, add sherwood oil (2000～6000 milliliters of/mole butyric acid) and water (200～600 milliliters of/mole butyric acid) again, being warming up to 40～80 ℃ feeds fluorine Lyons-22 (1-4 moles/mole butyric acid) again and reacts, with the reaction mixture dilute with water, water layer is used the concentrated hydrochloric acid acidifying after with petroleum ether, use the vinyl acetic monomer extracting again 3 times, merge organic layer, again it is washed with water, and filter with anhydrous magnesium sulfate drying, boil off the vinyl acetic monomer solvent, use 1: 0.6～1 methylene dichloride and normal hexane mixed solvent recrystallization again, the unreacted 2-of elimination white precipitate shape (4-hydroxy phenyl)-3 Methylbutanoic acid again with the filtrate evaporate to dryness, gets 2-(4-difluoro-methoxy the phenyl)-3 Methylbutanoic acid of yellow solid shape;
(3) adding mol ratio in the reactor that prolong and calcium chloride tube are housed is 2-(4-difluoro-methoxy phenyl)-3 Methylbutanoic acid and phosphorus trichloride of 1: 0.4～0.7, be warming up to 60～100 ℃ of reactions 1～3 hour, remove the phosphorous acid of remaining phosphorus trichloride and generation, get light yellow transparent liquid 2-(4-difluoro-methoxy phenyl)-3-methylbutyryl chlorine;
(4) mol ratio by 1: 1: 0.05～0.10 adds 2-(4-difluoro-methoxy phenyl)-3-methylbutyryl chlorine in the reactor of whipping appts is housed, behind 3-phenoxy benzaldehyde and the triethyl benzyl ammonia chloride, add toluene (500～2000 milliliters of/mole acyl chlorides) again, temperature control drips sodium cyanide solution (1～3 moles/mole acyl chlorides) between 5～25 ℃, continue to be stirred to and react completely, then reaction mixture is told organic layer, its water layer is incorporated organic layer into behind the methylbenzene extraction 3 times, use 5% hydrochloric acid again, water and saturated common salt water washing, and with anhydrous magnesium sulfate drying, boil off toluene solvant, get product fluoro-Cyano chrysanthemate of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105866 CN1010942B (en) | 1988-02-01 | 1988-02-01 | Synthetic process for fluoro-cyano chrysanthemate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105866 CN1010942B (en) | 1988-02-01 | 1988-02-01 | Synthetic process for fluoro-cyano chrysanthemate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034708A CN1034708A (en) | 1989-08-16 |
| CN1010942B true CN1010942B (en) | 1990-12-26 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105866 Expired CN1010942B (en) | 1988-02-01 | 1988-02-01 | Synthetic process for fluoro-cyano chrysanthemate |
Country Status (1)
| Country | Link |
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| CN (1) | CN1010942B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061212C (en) * | 1994-01-05 | 2001-01-31 | 上海中西药业公司 | Pesticide and mite-killing agent containing optically active compound and its preparation method |
| CN112457171B (en) * | 2020-12-14 | 2021-05-14 | 深圳市迪克曼科技开发有限公司 | Synthetic method of hydroxytyrosol |
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1988
- 1988-02-01 CN CN 88105866 patent/CN1010942B/en not_active Expired
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| Publication number | Publication date |
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| CN1034708A (en) | 1989-08-16 |
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