CN102020564A - Fluoro-containing cyclopropane carboxylate with acetylenic bond and preparation method and use thereof - Google Patents
Fluoro-containing cyclopropane carboxylate with acetylenic bond and preparation method and use thereof Download PDFInfo
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- CN102020564A CN102020564A CN2009101958036A CN200910195803A CN102020564A CN 102020564 A CN102020564 A CN 102020564A CN 2009101958036 A CN2009101958036 A CN 2009101958036A CN 200910195803 A CN200910195803 A CN 200910195803A CN 102020564 A CN102020564 A CN 102020564A
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Abstract
Fluoro-containing cyclopropane carboxylate with acetylenic bond, wherein the chemical name thereof is (2,3,5,6-tetrafluoro-4-methoxymethyl phenyl)-methyl-(1R)trans-2,2-dimethyl-3-(2-acetenyl-3-methoxy-3-oxypropyl)cyclopropane carboxylate, the compound can be used as active ingredients of farm chemical and pesticide with good insecticidalactivity.
Description
Technical field
The present invention relates to a kind of fluorine-containing cyclopropanecarboxylcompound with acetylene bond, also relate to Preparation Method And The Use, this compound is used to prevent and treat sanitary insect pest.
Background technology
The present invention relates to ester cpds and contain the active ingredient of this compound as agricultural chemicals.
There is the prospectus of the EP-31199A of EUROPEAN PATENT OFFICE known, the benzyl ester that the fluorine of some halogenated alkenyl cyclopropane-carboxylic acids replaces has insecticidal activity, and in these compounds, wherein the activity of the isomer of the ratios of the isomers transconfiguration that is cis-configuration at the 1-position and the substituting group on the 3-position of cyclopropane ring is higher.
Yet in pesticide composition, preventive effect and security all are important, therefore, in some use, from the angle of safety, use these compounds to be restricted usually.Pesticide composition especially for the prevailing disease control usually is to use in the restriceted envelope of living environment, and therefore, these compositions not only need desinsection or repellent activity, but also will comprise the people to Mammals, livestock and pet low toxicity.
Summary of the invention
The present invention is exactly in order to address the above problem, the benzyl ester pesticides that overcomes the fluorine replacement of halogenated alkenyl cyclopropane-carboxylic acid comprises people, livestock and the bigger problem of pet toxicity to Mammals, provide a kind of and more desinsection or repellent activity will be arranged, but also to comprise the people to Mammals, the compound of livestock and pet low toxicity.The applicant has carried out deep discovering, (2,3,5,6-tetrafluoro-4-methoxyl methyl phenyl)-methyl-(1R)-trans-(2,2-dimethyl-3-(2-ethynyl-3-methoxyl group-3-oxypropylene) cyclopropanecarboxylcompound shows the excellent insecticidal activity, and very safe to Mammals, based on this discovery, finished the present invention.This invention is applicable to that agricultural is economized production and the elimination sanitary insect pest uses.
The technical problem that will solve required for the present invention can be achieved through the following technical solutions:
As a first aspect of the present invention, a kind of fluorine-containing cyclopropanecarboxylcompound with acetylene bond, it is characterized in that, chemistry by name (2,3,5,6-tetrafluoro-4-methoxyl methyl phenyl)-methyl-(1R)-(2,2-dimethyl-3-(2-ethynyl-3-methoxyl group-3-oxypropylene) cyclopropanecarboxylcompound, structural formula is suc as formula shown in (I)
Described (2,3,5,6-tetrafluoro-4-methoxyl methyl phenyl)-methyl-(1R)-(2, the 1-position of the cyclopropane ring of 2-dimethyl-3-(2-ethynyl-3-methoxyl group-3-oxypropylene) cyclopropanecarboxylcompound and the steric configuration between the substituting group on the 3-position are trans,
In formula (I) compound, the 1-position of cyclopropane ring and the substituting group on the 3-position are the transconfiguration relation each other.Then, it must be essentially no cis type compound that The compounds of this invention is not necessarily wanted, and it also can be cis and trans mixture, as long as it is rich in the transconfiguration isomer.For example, this compound contains the mixture of isomers of the trans body of 80%-100%.
As a second aspect of the present invention, a kind of preparation method of the fluorine-containing cyclopropanecarboxylcompound with acetylene bond, it is characterized in that, trans 3-shown in the through type (II) (2-ethynyl-3-methoxyl group-3-oxypropylene)-2,2-dimethyl cyclopropane carboxylic acid or its active derivative, with (2 shown in the formula (III), 3,5,6-tetrafluoro-4-methoxyl methyl phenyl) methyl alcohol or its active derivatives reaction presentation in next life (I) compound, in organic solvent, catalysts carries out under existing, and the reaction times is between 5 minutes-72 hours; The temperature range of reaction is usually between 80 ℃ 200 ℃; The perhaps boiling temperature of 80 ℃ of used solvents to the reaction;
The alkylol cpd of the carboxylic acid cpd of formula (II) or its active derivative and formula (III) or the mol ratio of its active derivative can not be subjected to anyly restrictedly to select, and wait mole or near 1: 1 mol ratio but be preferably.
Wherein, the active derivative of formula (II) carboxylic acid cpd is an acyl chlorides, acid anhydrides, C1-C4 alkyl ester.Carboxylic acid cpd shown in the formula (II) or its active derivative, for example can mention following compounds:
Trans 3-(2-ethynyl-3-methoxyl group-3-oxypropylene)-2, the 2-dimethyl cyclopropane carboxylic acid;
Trans 3-(2-ethynyl-3-methoxyl group-3-oxypropylene)-2,2-dimethylcyclopropane carboxyl acyl chloride.
Wherein, the active derivative of formula (III) alkylol cpd is its halogenide, sulphonate, quaternary ammonium salt.As for the alkylol cpd shown in the formula (III) or its active derivative, for example can mention following compounds:
(2,3,5,6-tetrafluoro-4-methoxyl methyl phenyl) methyl alcohol;
1-chloromethyl-2,3,5,6-tetrafluoro-4-methoxyl methyl benzene;
1-brooethyl-2,3,5,6-tetrafluoro-4-methoxyl methyl benzene.
Wherein, catalysts comprises tertiary amine such as triethylamine, 4-Dimethylamino pyridine, diisopropyl ethyl amine etc.; Nitrogenous aromatic substance such as pyridine etc.; Alkali metal alcoholates such as sodium methylate, potassium tert.-butoxide etc.; Mineral alkali such as sodium hydroxide, salt of wormwood, sodium hydride etc.; Protonic acid such as tosic acid, sulfuric acid etc.; Lewis' acid such as phenoxide titanium (IV); With other reagent such as dicyclohexyl carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride, triphenylphosphine and diethylazodicarboxylate or diisopropyl azo-2-carboxylic acid's combination etc.
Wherein, solvent comprises hydro carbons such as benzene, toluene, dimethylbenzene etc., ethers such as ether, tetrahydrofuran (THF) etc.; Halohydrocarbon such as methylene dichloride, 1,2-ethylene dichloride etc.; Amides such as dimethyl formamide etc.; Ketone such as acetone etc.; Organosulfur type solution such as dimethyl sulfoxide (DMSO) etc.; And composition thereof.
After above-mentioned reaction is finished, liquid reaction mixture is carried out aftertreatment, adopt organic solvent extraction, concentrate acquisition formula (I) compound.
After perhaps above-mentioned reaction is finished, liquid reaction mixture is carried out aftertreatment, by chromatogram, distillation, recrystallization operation purifying obtains formula (I) compound.
As third aspect present invention, a kind of application of fluorine-containing cyclopropanecarboxylcompound on pest control of above-mentioned band acetylene bond.
Wherein, comprise formula (I) compound to Agricultural pests and significant quantity that sanitary insect pest is used.
Beneficial effect of the present invention:
Formula (I) compound (2,3,5,6-tetrafluoro-4-methoxyl methyl phenyl)-methyl-(1R)-trans-(2,2-dimethyl-3-(2-ethynyl-3-methoxyl group-3-oxypropylene) cyclopropanecarboxylcompound shows the excellent insecticidal activity, and very safe to Mammals.This invention is applicable to that agricultural is economized production and the elimination sanitary insect pest uses.
Embodiment
In order to make technique means of the present invention, creation characteristic, to reach purpose and effect is easy to understand,, further set forth the present invention below in conjunction with specific embodiment.
Embodiment 1
Under ice-cooled temperature, with 0.75g (1R)-trans 3-(2-ethynyl-3-methoxyl group-3-oxypropylene)-2,2-dimethylcyclopropane carboxyl acyl chloride (3.12mmol) joins 0.83g (2 in the 5ml toluene solution, 3,5,6-tetrafluoro-4-methoxyl methyl phenyl) methyl alcohol (3.71mmol), in the mixture of 15ml toluene and 0.5g pyridine, reaction is spent the night, and adds entry, and it is extracted with t-butyl methyl ether.Organic layer is concentrating under reduced pressure after dried over sodium sulfate.Resistates carries out column chromatography with n-hexane/ethyl acetate (20/1) mixture as eluent.Obtain 1.07g (2,3,5,6-tetrafluoro-4-methoxyl methyl phenyl)-methyl-(1R)-trans-2,2-dimethyl-3-(2-ethynyl-3-methoxyl group-3-oxypropylene) cyclopropanecarboxylcompound (productive rate: 80%).
Embodiment 2
Under ice-cooled temperature, with 2, the 6g diisopropyl azo-2-carboxylic acid in toluene 40% solution and the mixture of 10ml tetrahydrofuran (THF) join 1.16g (1RS)-trans 3-(2-ethynyl-3-methoxyl group-3-oxypropylene)-2,2-dimethyl cyclopropane carboxylic acid (5.22mmol), 1.12g (2,3,5,6-tetrafluoro-4-methoxyl methyl phenyl) methyl alcohol (5.0mmol) and 1.33g triphenylphosphine are in the solution of 40ml tetrahydrofuran (THF).Reaction is spent the night, with the reaction mixture concentrating under reduced pressure.Resistates carries out column chromatography with n-hexane/ethyl acetate (10/1) mixture as eluent.Obtain 1.8g (2,3,5,6-tetrafluoro-4-methoxyl methyl phenyl)-methyl-(1R)-trans-2,2-dimethyl-3-(2-ethynyl-3-methoxyl group-3-oxypropylene) cyclopropanecarboxylcompound (productive rate: 84%).
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (12)
1. the fluorine-containing cyclopropanecarboxylcompound with acetylene bond is characterized in that, chemistry by name (2,3,5,6-tetrafluoro-4-methoxyl methyl phenyl)-methyl-(1R)-(2,2-dimethyl-3-(2-ethynyl-3-methoxyl group-3-oxypropylene) cyclopropanecarboxylcompound, structural formula is suc as formula shown in (I)
2. a kind of fluorine-containing cyclopropanecarboxylcompound according to claim 1 with acetylene bond, it is characterized in that, described (2,3,5,6-tetrafluoro-4-methoxyl methyl phenyl)-methyl-(1R)-(2, the 1-position of the cyclopropane ring of 2-dimethyl-3-(2-ethynyl-3-methoxyl group-3-oxypropylene) cyclopropanecarboxylcompound and the steric configuration between the substituting group on the 3-position are trans, and this compound contains the mixture of isomers of the trans body of 80%-100%.
3. the preparation method of the fluorine-containing cyclopropanecarboxylcompound of a band acetylene bond as claimed in claim 1, it is characterized in that, trans 3-shown in the through type (II) (2-ethynyl-3-methoxyl group-3-oxypropylene)-2,2-dimethyl cyclopropane carboxylic acid or its active derivative, with (2 shown in the formula (III), 3,5,6-tetrafluoro-4-methoxyl methyl phenyl) methyl alcohol or its active derivatives reaction presentation in next life (I) compound, in organic solvent, catalysts carries out under existing, and the reaction times is between 5 minutes-72 hours; The temperature range of reaction is usually between 80 ℃ to 200 ℃;
4. preparation method according to claim 3 is characterized in that, the carboxylic acid cpd of described formula (II) or its active derivative and the alkylol cpd of formula (III) or the mol ratios such as mol ratio of its active derivative.
5. preparation method according to claim 3 is characterized in that, the active derivative of described formula (II) carboxylic acid cpd is an acyl chlorides, acid anhydrides, C
1-C
4Alkyl ester.
6. preparation method according to claim 3 is characterized in that, the active derivative of described formula (III) alkylol cpd is its halogenide, sulphonate, quaternary ammonium salt.
7. preparation method according to claim 3 is characterized in that, described catalysts is tertiary amine such as triethylamine, 4-Dimethylamino pyridine, any one of diisopropyl ethyl amine or more than one combinations.
8. preparation method according to claim 3 is characterized in that described solvent comprises hydro carbons such as benzene, toluene, dimethylbenzene, ethers such as ether, tetrahydrofuran (THF); Halohydrocarbon such as methylene dichloride, 1, the 2-ethylene dichloride; Amides such as dimethyl formamide; Ketone such as acetone; Organosulfur type solution such as dimethyl sulfoxide (DMSO); And composition thereof.
9. preparation method according to claim 3 is characterized in that, after described reaction is finished, liquid reaction mixture is carried out the aftertreatment organic solvent extraction, concentrates acquisition formula (I) compound.
10. preparation method according to claim 3 is characterized in that, after described reaction is finished, liquid reaction mixture is carried out aftertreatment, by chromatogram, and distillation, recrystallization operation purifying obtains formula (I) compound.
11. the application of fluorine-containing cyclopropanecarboxylcompound on pest control of a band acetylene bond as claimed in claim 1.
12. application according to claim 11 is characterized in that, comprises formula (I) compound to Agricultural pests and significant quantity that sanitary insect pest is used.
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| CN2009101958036A CN102020564A (en) | 2009-09-17 | 2009-09-17 | Fluoro-containing cyclopropane carboxylate with acetylenic bond and preparation method and use thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485564A (en) * | 2018-11-28 | 2019-03-19 | 赵学迅 | A kind of new method preparing Biphenthrin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0031199A1 (en) * | 1979-12-21 | 1981-07-01 | Imperial Chemical Industries Plc | Substituted benzyl esters of cyclopropane carboxylic acids and their preparation, compositions containing them and methods of combating insect pests therewith, and substituted benzyl alcohols |
| CN1148379A (en) * | 1995-02-07 | 1997-04-23 | 大日本除虫菊株式会社 | Novel carboxylic ester derivatives, process for producing same, and insecticide or insectifuge contg. same |
| CN1306958A (en) * | 2000-01-26 | 2001-08-08 | 住友化学工业株式会社 | Cyclopropane carboxylic ester compound |
| CN1648119A (en) * | 2004-01-20 | 2005-08-03 | 江苏扬农化工股份有限公司 | Several new pyrethroid compounds |
| WO2009082018A1 (en) * | 2007-12-21 | 2009-07-02 | Sumitomo Chemical Company, Limited | Cyclopropanecarboxylate and pest controlling composition containing the same |
-
2009
- 2009-09-17 CN CN2009101958036A patent/CN102020564A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0031199A1 (en) * | 1979-12-21 | 1981-07-01 | Imperial Chemical Industries Plc | Substituted benzyl esters of cyclopropane carboxylic acids and their preparation, compositions containing them and methods of combating insect pests therewith, and substituted benzyl alcohols |
| CN1148379A (en) * | 1995-02-07 | 1997-04-23 | 大日本除虫菊株式会社 | Novel carboxylic ester derivatives, process for producing same, and insecticide or insectifuge contg. same |
| CN1306958A (en) * | 2000-01-26 | 2001-08-08 | 住友化学工业株式会社 | Cyclopropane carboxylic ester compound |
| CN1648119A (en) * | 2004-01-20 | 2005-08-03 | 江苏扬农化工股份有限公司 | Several new pyrethroid compounds |
| WO2009082018A1 (en) * | 2007-12-21 | 2009-07-02 | Sumitomo Chemical Company, Limited | Cyclopropanecarboxylate and pest controlling composition containing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485564A (en) * | 2018-11-28 | 2019-03-19 | 赵学迅 | A kind of new method preparing Biphenthrin |
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Application publication date: 20110420 |