CN101367722B - Preparation of pyrethroid midbody - Google Patents
Preparation of pyrethroid midbody Download PDFInfo
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- CN101367722B CN101367722B CN2008100689413A CN200810068941A CN101367722B CN 101367722 B CN101367722 B CN 101367722B CN 2008100689413 A CN2008100689413 A CN 2008100689413A CN 200810068941 A CN200810068941 A CN 200810068941A CN 101367722 B CN101367722 B CN 101367722B
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Abstract
The invention relates to a preparation method of the intermediate of pyrethroid, the chemical name is 3-(3,3,3-trifluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid. The preparation method has following procedures: 3-(3,3,3-trifluoro-1- propargyl)-2,2-dimethyl cyclopropane carboxylic acid ester is reduced to prepare 3-(3,3,3-trifluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid methyl ester, and then saponified and acidified to prepare 3-(3,3,3- trifluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid, and then chloridized by acyl and esterified to obtain septenary-fluorine methothrin (2,3,5,6-tetra-fluorine-4-methoxymethyl benzyl 3-(3,3,3- trifluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester). The procedure of the method is reasonable, simple, safe and reliable, and the overall yield of the product is high and the purity is high; the preparation method has wide industrial application prospect.
Description
Technical field: the invention belongs to the organic insecticide field, specifically relate to a kind of pyrethroid synthetic trifluoro cyclopropane-carboxylic acid that is applied to, chemical name 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid's preparation method, it is the important intermediate of preparation pyrethroid.
Background technology: for a long time, 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester is a by product of pyrethroid intermediate process, because of structure does not have drug effect, wastes unfortunately as a kind of waste product, the inventor is through research, with 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester is processed into 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl alkane propane carboxylic acid, promptly can be used as an intermediate raw material of synthetic a kind of new pesticides seven fluorine s, and new pesticides seven fluorine s not only have better desinsection and miticidal effect but also low to human toxicity than tefluthrin.The method of closing of seven fluorine first chrysanthemum esters such as patent application " a kind of pyrethroid compound intermediates preparation " application number 200310121742.1
Summary of the invention: purpose of the present invention, be to utilize a by product 3-(3 of pyrethroid intermediate process, 3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester is prepared into a kind of intermediate 3-(3 of new pyrethroid (seven fluorine s), 3,3-three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid is turned waste into wealth.
The present invention finishes through two steps:
(1) with 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester is that raw material makes 3-(3,3,3-three fluoro-1-propenyl)-2 through hydrogen reduction, and 2-dimethyl cyclopropane carboxylic acid ester is called for short the trifluoromethyl cyclopropanecarboxylcompound;
(2) the trifluoromethyl cyclopropanecarboxylcompound is got 3-(3,3,3-three fluoro-1-propenyl)-2 through the saponification acidifying, 2-dimethylpropane carboxylic acid is called for short the trifluoromethyl cyclopropane-carboxylic acid, and its reaction process is as follows:
(I) is 3-(3,3,3-three fluoro-1-proyls)-2 in the formula, 2-dimethyl cyclopropane carboxylic acid ester; (II) is 3-(3,3,3-three fluoro-1-propenyl)-2, and 2-dimethyl cyclopropane carboxylic acid ester is called for short the trifluoromethyl cyclopropanecarboxylcompound; (III) is 3-(3,3,3-three fluoro-1-propenyl)-2, and the 2-dimethyl cyclopropane carboxylic acid is called for short the trifluoromethyl cyclopropane-carboxylic acid.
The R that mentions in the formula is respectively the straight or branched alkyl of 1---6 carbon atom, is preferably methyl, ethyl, n-propyl, normal-butyl, n-pentyl, sec.-propyl, isobutyl-, the tertiary butyl or neo-pentyl.Methyl more preferably.Promptly be methylic 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid methyl esters.
The present invention to the method that above-mentioned two steps provide is:
(1) with 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester is a raw material, being reductive agent with hydrogen, with alcohols, aromatic hydrocarbon, ethers, organic acid or ester such as methyl alcohol, ethanol, Virahol, ethylene glycol, polyoxyethylene glycol or tetrahydrofuran (THF) etc. are solvent, with metal, metal oxide, mixed metal oxide, metal-salt or metal complex such as palladium carbon, alumino nickels etc. are catalyzer, 30～150 ℃ of temperature of reaction, 3～30 hours reaction times is under reaction pressure 0.1～3Mpa condition, make 3-(3 through catalytic reduction reaction, 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester.
When making reductive agent with hydrogen, should be added with palladium metal, the palladium metal alumina mixture, mixed metal oxide, the whole compound of metal-salt or metal is made catalyzer, as palladium carbon or alumino nickel.
Organic solvent also comprises aromatic hydrocarbon such as toluene except that above-mentioned solvent, dimethylbenzene, and 1,2-dimethanol or Virahol and aromatic mixed solvent, the processing of carrying out after the reduction reaction:
A, filtering separation reclaim catalyzer.
B, distillating recovering solvent.
C, distill product.
(2) with the method that gets the trifluoromethyl cyclopropane-carboxylic acid after the saponification acidifying of trifluoromethyl cyclopropane carboxylic acid ester footpath be: with the trifluoromethyl cyclopropanecarboxylcompound is raw material, in the presence of organic solvents such as methyl alcohol or ethanol or Virahol, with 50～90 ℃ of liquid caustic soda or sheet alkali reaction temperature of reaction, 4～6 hours reaction times, after reaction is finished, steam organic solvent, add hydrochloric acid then, nitric acid or sulfuric acid acidation, then with toluene, dimethylbenzene, hexanaphthene, a kind of in the sherwood oil is extraction agent, extract the trifluoromethyl cyclopropane-carboxylic acid, reclaim organic extractant through precipitation and obtain trifluoromethyl cyclopropane-carboxylic acid of the present invention, be i.e. product in the middle of the pyrethroid of indication of the present invention.
The pyrethroid intermediates can be retained in the solvent without extraction, directly enter next step reaction, can shorten the step of reaction.
The present invention simultaneously by following step with 3-(3,3,3-three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid is converted into seven fluorine s:
1) 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid chloride obtains 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides.
2) with 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides and 2,3,5,6-tetrafluoro-4-methoxymethyl benzylalcohol esterification obtains seven fluorine s.
Its reaction process is as follows:
(IV) 3-in the formula (3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides is called for short trifluoromethyl cyclopropane carboxylic acid isoxazolecarboxylic acid, and (V) is 2,3,5,6-tetrafluoro-4-methoxymethyl benzylalcohol, (VI) is 2,3,5,6-tetrafluoro-4-methoxymethyl 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester is called for short seven fluorine s.
Wherein 2) method of the esterification process of seven fluorine s is: remove hydrogen chloride gas by the physics method, as heating, vacuumize or blowing of rare gas element caught up with; The chemical method available bases is as pyridine, liquid caustic soda or soda ash neutralization.Esterification is as using 3-(3,3,3-three fluoro-1-propenyl)-2, and the 2-dimethyl cyclopropane carboxylic acid can use solvent to dewater under the strongly acidic catalyst effect, and band water is finished reaction.
The present invention has not only effectively utilized a synthetic byproduct that removes lacca intermediate process, turn waste into wealth, and utilize byproduct 3-(3,3,3-three fluoro-1-proyls)-2, the intermediate raw material that 2-dimethyl cyclopropane carboxylic acid ester is made is produced a kind of new pyrethroid, i.e. seven fluorine s, and all the tefluthrin than common production is good at desinsection and miticidal effect, low to human toxicity, in addition, no matter technology of the present invention is intermediate and the finished product in the process of producing seven fluorine s, production process route is reasonable, simple to operate, production safety is reliable, and toxicity is low, reduced the influence of environment, and the yield height, the purity height is a kind of preparation method with wide prospects for commercial application.
The present invention is further illustrated below by following example.
Embodiment:
Embodiment 1
(1) in the autoclave of 1000ml, add 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester 110g, active palladium carbon 5g, methyl alcohol 400ml feeds hydrogen reducing under 30～40 ℃ of temperature condition, and pressure condition is 1～2Mpa.Question response does not cool to room temperature after having tangible absorption, emptying, and discharging, suction filtration removes palladium carbon, and filtrate negative pressure precipitation gets 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester 108g, content 97.5%, yield are 95%.
(2) have the four-hole bottle of condenser at a 2000ml, drop into 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester 110g, 30% liquid caustic soda 73g, methyl alcohol 300g stir, and are warmed up to 60～70 ℃ of backflows then, be incubated 6 hours, reaction is finished, and steams methyl alcohol.Add hcl acidifying PH=2, add solvent, as 300 milliliters of extractions of toluene, the oil reservoir washing, precipitation reclaims toluene, gets 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 100.6g.Content is 98%, yield 94.8%.Above-mentioned liquid caustic soda is meant sodium hydroxide or potassium hydroxide aqueous solution.
Embodiment 2
(1) in the autoclave of 1000ml, add 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester 110g, active alumino nickel 4g, methyl alcohol 400ml feeds hydrogen reducing under 80～100 ℃ of temperature condition, and pressure condition is 0.3～1Mpa.Question response does not cool to room temperature after having tangible absorption, emptying, and discharging, suction filtration removes alumino nickel, and filtrate negative pressure precipitation gets 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester 104.6g, content 95.5%, yield are 90%.
(2) have the four-hole bottle of condenser at a 2000ml, drop into 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester 110g, 30% liquid caustic soda 60g, ethanol 300g stir, and are warmed up to 70～90 ℃ of backflows then, be incubated 4 hours, reaction is finished, and steams ethanol.Add hcl acidifying PH=2, add solvent, as 250 milliliters of extractions of hexanaphthene, the oil reservoir washing, precipitation reclaims hexanaphthene, gets 3-(3,3,3-three fluoro-1-propenyl)-2, and 2-dimethyl cyclopropane carboxylic acid 102.6g, content are 94%, yield 92.8%.
Embodiment 3
(1) in the autoclave of 1000ml, add 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester 110g, active palladium carbon 10g, methyl alcohol 200ml feeds hydrogen reducing under 40～60 ℃ of temperature condition, and pressure condition is 2～3Mpa.Question response does not cool to room temperature after having tangible absorption, emptying, and discharging, suction filtration removes palladium carbon, and filtrate negative pressure precipitation gets 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester 106.9g, content 97.6%, yield are 94%.
(2) have the four-hole bottle of condenser at a 2000ml, drop into 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester 110g, sodium hydroxide or potassium hydroxide pellets alkali 50g, Virahol 500g stir, be warmed up to 60～70 ℃ of backflows then, be incubated 5 hours, reaction is finished, and steams Virahol.Add hcl acidifying PH=2, the adding solvent, as 500 milliliters of sherwood oils, extraction extraction at twice, the oil reservoir washing, precipitation reclaims sherwood oil, gets 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 98.2g.Content is 96.1%, yield 90.8%.
Embodiment 4
The preparation of seven fluorine s
The first step: synthetic 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides
At the four-hole bottle of a 500ml, drop into 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 104g, toluene 80g stir, be warmed up to 50～70 ℃ of backflows then, dripping thionyl chloride 60g drips insulation 2～3 hours, reaction is finished, steam unnecessary sulfur oxychloride and part toluene, get 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides.Must measure 119.4g, content is 90%, yield 94.8%.
Second step: synthetic seven fluorine s
At the four-hole bottle of a 1000ml, add lysed 2,3,5,6-tetrafluoro-4-methoxymethyl benzylalcohol 112g adds pyridine 40g, agitation and dropping 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 115g drips insulation 4 hours, and reaction is finished, cool to 50 ℃, add water-soluble salt, wash once, esterifying liquid is sloughed toluene and is got seven fluorine s.Must measure 120g, content is 95%, yield 94.8%.
The applicant has invented a kind of new preparation method of intermediate of pyrethroid compound, this intermediate 3-(3,3,3-three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid, and then obtaining seven fluorine s by chloride, esterification, this technology has the advantages that operational path is simple, safe and reliable, mass yield is high, cost is low.Be fit to suitability for industrialized production.
Claims (6)
1. a pyrethroid intermediate 3-(3,3,3-three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid, be called for short: the preparation method of trifluoromethyl cyclopropane-carboxylic acid, structural formula:
It is characterized in that (1) is with 3-(3,3,3-three fluoro-1-proyls)-2,2-dimethyl cyclopropane carboxylic acid ester is a raw material, is reductive agent with hydrogen, with any solvent of doing of alcohols, arene, ethers, organic acid or ester, with palladium carbon or alumino nickel is catalyzer, 30～150 ℃ of temperature of reaction, 3～30 hours reaction times is under reaction pressure 0.1～3Mpa condition, make 3-(3 through catalytic reduction reaction, 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester; (2) be raw material with the trifluoromethyl cyclopropanecarboxylcompound then, in the presence of organic solvent, with liquid caustic soda or sheet alkali soapization, 50～90 ℃ of saponification reaction temperature, 4～6 hours reaction times is after reaction is finished, steam organic solvent, use acidifying then, to get the trifluoromethyl cyclopropane-carboxylic acid after the extraction agent extraction, its reaction process is as follows then:
Following formula (1) and (II) in R represent: the straight or branched alkyl of 16 carbon atoms.
2. according to the preparation method of the described a kind of trifluoromethyl cyclopropanecarboxylcompound of claim 1, it is characterized in that being formula (I) and (II) in R be methyl, ethyl, n-propyl, n-pentyl, sec.-propyl, isobutyl-, the tertiary butyl or neo-pentyl.
3. according to the preparation method of the described a kind of trifluoromethyl cyclopropanecarboxylcompound of claim 1, it is characterized in that being that R is a methyl.
4. according to the preparation method of claim 1 or 2 described a kind of trifluoromethyl cyclopropanecarboxylcompounds, it is characterized in that being that solvent is: methyl alcohol, ethanol, Virahol, ethylene glycol, polyoxyethylene glycol or tetrahydrofuran (THF).
According to the described a kind of trifluoromethyl cyclopropanecarboxylcompound of claim 1 the preparation method, it is characterized in that the solvent that reacts used is methyl alcohol, ethanol; Extracting used extraction agent is, a kind of in toluene, dimethylbenzene, hexanaphthene, the sherwood oil, and the mole proportioning of trifluoromethyl cyclopropanecarboxylcompound and extraction agent is 1: 2～5; Used alkali is: a kind of in liquid caustic soda, the sheet alkali; Used acid is a kind of in hydrochloric acid, sulfuric acid, the nitric acid.
According to the described a kind of trifluoromethyl cyclopropanecarboxylcompound of claim 1 the preparation method, it is characterized in that the trifluoromethyl cyclopropane-carboxylic acid again through obtaining seven fluorine s after chloride, the esterification, can be converted into seven fluorine s with the trifluoromethyl cyclopropane-carboxylic acid by following step:
1) chloride of trifluoromethyl cyclopropane-carboxylic acid is obtained trifluoromethyl cyclopropane carboxylic acid isoxazolecarboxylic acid;
2) with trifluoromethyl cyclopropane carboxylic acid isoxazolecarboxylic acid and 2,3,5,6-tetrafluoro-4-methoxymethyl benzylalcohol esterification obtains seven fluorine s.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100584817C (en) * | 2008-10-14 | 2010-01-27 | 江苏扬农化工股份有限公司 | Pyrethroid compound and uses |
| CN101367730A (en) * | 2008-10-16 | 2009-02-18 | 贵阳柏丝特化工有限公司 | Pyrethroid and synthesis thereof |
| CN102086154A (en) * | 2010-12-18 | 2011-06-08 | 浙江大学 | Pyrethroid intermediate and synthesis method thereof |
| CN109651145A (en) * | 2019-01-17 | 2019-04-19 | 江苏春江润田农化有限公司 | The synthetic method of trifluoro ynoic acid methyl ester |
| CN109761807A (en) * | 2019-01-17 | 2019-05-17 | 江苏春江润田农化有限公司 | The preparation method of trifluoro ynoic acid methyl ester |
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