CN108250078A - A kind of pyrethroid compound - Google Patents
A kind of pyrethroid compound Download PDFInfo
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- CN108250078A CN108250078A CN201611245078.5A CN201611245078A CN108250078A CN 108250078 A CN108250078 A CN 108250078A CN 201611245078 A CN201611245078 A CN 201611245078A CN 108250078 A CN108250078 A CN 108250078A
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- Prior art keywords
- compound
- pyrethroid
- pyrethroid compound
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- dimethyl
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 72
- 239000002728 pyrethroid Substances 0.000 title claims abstract description 45
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- -1 acetyl halide compound Chemical class 0.000 claims description 19
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical class FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- 241000238631 Hexapoda Species 0.000 claims description 12
- 238000009472 formulation Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 9
- 230000002265 prevention Effects 0.000 claims description 9
- 239000004480 active ingredient Substances 0.000 claims description 6
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 claims description 6
- 241000255925 Diptera Species 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 241001674044 Blattodea Species 0.000 claims description 2
- 241000488583 Panonychus ulmi Species 0.000 claims description 2
- 241000344246 Tetranychus cinnabarinus Species 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000000749 insecticidal effect Effects 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000000443 aerosol Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000000857 drug effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 241000500437 Plutella xylostella Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001289510 Attagenus unicolor Species 0.000 description 2
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 2
- 241000723353 Chrysanthemum Species 0.000 description 2
- 235000007516 Chrysanthemum Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005903 Gamma-cyhalothrin Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- NYPJDWWKZLNGGM-UHFFFAOYSA-N fenvalerate Chemical compound C=1C=C(Cl)C=CC=1C(C(C)C)C(=O)OC(C#N)C(C=1)=CC=CC=1OC1=CC=CC=C1 NYPJDWWKZLNGGM-UHFFFAOYSA-N 0.000 description 2
- ZXQYGBMAQZUVMI-GCMPRSNUSA-N gamma-cyhalothrin Chemical compound CC1(C)[C@@H](\C=C(/Cl)C(F)(F)F)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-GCMPRSNUSA-N 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229960000490 permethrin Drugs 0.000 description 2
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- AGWVQASYTKCTCC-UHFFFAOYSA-N (2,3,5,6-tetrafluorophenyl)methanol Chemical compound OCC1=C(F)C(F)=CC(F)=C1F AGWVQASYTKCTCC-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 235000006008 Brassica napus var napus Nutrition 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 241001674939 Caulanthus Species 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KVIZNNVXXNFLMU-AIIUZBJTSA-N [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl (1r,3r)-2,2-dimethyl-3-[(e)-prop-1-enyl]cyclopropane-1-carboxylate Chemical compound FC1=C(F)C(COC)=C(F)C(F)=C1COC(=O)[C@H]1C(C)(C)[C@@H]1\C=C\C KVIZNNVXXNFLMU-AIIUZBJTSA-N 0.000 description 1
- OOWCJRMYMAMSOH-UHFFFAOYSA-N [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound FC1=C(F)C(COC)=C(F)C(F)=C1COC(=O)C1C(C)(C)C1C=C(C)C OOWCJRMYMAMSOH-UHFFFAOYSA-N 0.000 description 1
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- YMGUBTXCNDTFJI-UHFFFAOYSA-M cyclopropanecarboxylate Chemical compound [O-]C(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-M 0.000 description 1
- QQODLKZGRKWIFG-QSFXBCCZSA-N cyfluthrin Chemical compound CC1(C)[C@@H](C=C(Cl)Cl)[C@H]1C(=O)O[C@@H](C#N)C1=CC=C(F)C(OC=2C=CC=CC=2)=C1 QQODLKZGRKWIFG-QSFXBCCZSA-N 0.000 description 1
- 229960001591 cyfluthrin Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003255 drug test Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002024 ethyl acetate extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 230000003285 pharmacodynamic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical class [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical class ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000001018 virulence Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
- C07C69/747—Chrysanthemumic acid esters
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of pyrethroid compounds, and the structural formula of the compound is as shown in formula A；The compound chrysanthemumic acid part is 1R, and trans- single optical isomer, wherein R is H atom or methyl；Compared with prior art, the compound of the present invention has better insecticidal effect to certain particular target pests；
Description
Technical field
The present invention relates to a kind of pyrethroid compound, the pyrethroid of especially a kind of specific spatial configuration
Close the application in object and preparation method thereof and control of insect.
Background technology
Pyrethroid coumpound is the insecticide of a kind of bio-mimetic syntheses, can be used for various pests, and with compared with
High insecticidal activity.Pyrethroid coumpound has the characteristics that efficient, low toxicity, low-residual, environment compatibility are good, in pest
Prevention and control field be widely used.
Prior art discloses a variety of pyrethroid coumpounds, such as cyfluthrin, fenvalerate, although this kind ofization
Closing object has good insecticidal activity, but with long-term continuous single use, pest produces pesticide drug resistance, therefore needs
Develop new compound.
On the other hand as requirement of the people to environmental protection is higher and higher, the high bioactivity body of pesticide increasingly causes people
Attention, pyrethroid usually has 2~8 optical isomers, and bioactivity is widely different between Isomers, it is therefore desirable to
Research prepares the isomers of most highly active.From the point of view of environmental protection, it can not dropped using the single optical isomer of high activity
The dose of application is reduced under the premise of low drug effect, so as to reduce the toxicity to non-target organism, improves safety, reduces residual medicine
Substance environment pollutes.
However the new pyrethroid compounds of old kind can be surmounted to obtain the aspects such as drug effect, toxicity, cost
Become more and more difficult.Since this century, the development progress of pyrethroid noval chemical compound is slow, and obtaining industrialization should
Only dimefluthrin, the metofluthrin of SUMITOMO CHEMICAL Chemical Co., Ltd.；Jiangsu Province, China raises agrochemicals share
A few new varieties such as the fluorine chlorine ether chrysanthemum ester of Co., Ltd.
This technology inventor has found that ICI companies exist in the studying for a long period of time of pyrethroid insecticides
In US4370346A and SUMITOMO CHEMICAL chemical company refers to one kind in JP2000239232 and contains difluoro chrysanthemumic acid structure
Pyrethroid compound, this kind of fluorine-containing insecticide can preferably overcome the interaction between old pyrethroid to resist
Property.The present inventor is by further investigation, it is proposed that the pyrethroid compound of this specific spatial configuration of the present invention,
The compound has excellent prevention drug effect to certain particular target pests.
Invention content
The technical problems to be solved by the invention are to be directed to the deficiencies in the prior art, and provide a kind of pyrethroid
Ester compounds, the compound are the pyrethroid Pesticidal compounds of the high activity of specific stereochemical structure.
The second object of the present invention is to provide a kind of preparation method of the pyrethroid compound.
The third object of the present invention is to provide a kind of application of pyrethroid compound in pest control.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of pyrethroid compound, structure is as shown in formula A：
R in formula is selected from H atom or methyl.
In above-mentioned technical proposal, when the R is H atom, which is 2,3,5,6- ptfe benzyl -2,2- diformazans
Trans--the 3- of base -1R- (2,2- difluoroethylenes base) cyclopropanecarboxylcompound.
In above-mentioned technical proposal, when the R is methyl, which is 2,3,5,6- tetra- fluoro- 4- methylbenzyls -2,2-
Trans--the 3- of dimethyl -1R- (2,2- difluoroethylenes base) cyclopropanecarboxylcompound.
The present invention also provides a kind of preparation methods of the pyrethroid compound：2,2- dimethyl -1R- is trans- -
3- (2,2- difluoroethylene base) cyclopropane-carboxylic acids or its corresponding acetyl halide compound, in organic solvent, and 2,3,5,6- tetrafluoros
Benzylalcohol or 2,3,5,6- tetrafluoros carry out esterification to xylyl alcohol, so as to obtain the pyrethroid compound；
Described trans--the 3- of 2,2- dimethyl -1R- (2,2- difluoroethylenes base) cyclopropane-carboxylic acid/its corresponding carboxylic acid halides
Close object, and 2,3,5,6- tetrafluorobenzyl alcohols/2,3,5,6- tetrafluoros are 0.8 to the molar ratio of xylyl alcohol：1~1.2：1；
The temperature of the esterification is the boiling under reflux temperature of the organic solvent；
Described trans--the 3- of 2,2- dimethyl -1R- (the 2,2- difluoroethylenes base) cyclopropane-carboxylic acid can be in background technology
Prepared by technology of the ICI companies of description disclosed in US4370346A patents, can also be according to the method in the embodiment of the present invention
It prepares.
The present invention also provides a kind of pyrethroid compound in terms of prevention sanitary insect pest or agricultural pests
Application.
In above-mentioned technical proposal, the sanitary insect pest is mosquito, fly, moth or blattaria etc..
In above-mentioned technical proposal, the agricultural pests are Tetranychus cinnabarinus or red spider etc..
In above-mentioned technical proposal, the pyrethroid compound is prepared into conventional formulation so as to use as active ingredient
In prevention sanitary insect pest or agricultural pests；
When the pyrethroid compound is prepared into conventional formulation as active ingredient, conventional formulation includes described
Pyrethroid compound is in itself or including the pyrethroid compound and inert carrier；
When the conventional formulation includes the pyrethroid compound and inert carrier, pyrethroid compound
Weight account for the 0.001~95% of conventional formulation total weight；
The conventional formulation can prepare the conventional formulation by following method：
1. pyrethroid compound of the present invention is mixed with liquid and/or carrier gas, and it is optionally added preparation use
Surfactant and other adjuvants；
2. pyrethroid compound of the present invention is mixed with powdery solid carrier, and it is optionally added preparation and is lived with surface
Property agent and other adjuvants；Or
3. with the solid carrier of pyrethroid compound dip mold of the present invention；Or the compounds of this invention and powdery are consolidated
Body carrier mixes, and is optionally added preparation surfactant and other adjuvants, and obtained mixture is shaped.
The pyrethroid compound of this specific spatial configuration of the present invention, the compound is to certain particular target pests
With excellent prevention drug effect.
Specific embodiment
Explain in detail technical solutions and effects of the present invention in the form of examples below, but the present invention is not limited to following
Embodiment.Following % contents refer both to mass fraction without specified otherwise.
2,2- dimethyl -1R, the synthesis of trans- -3- (2- the methyI-oropvDs)-cyclopropyl-carboxylic acids tert-butyl ester, that is, compound 1：
In the four round flask of the 1L with stirring, 200g anhydrous tetrahydro furans, 56g potassium tert-butoxides are added in.By 50g
2,2- dimethyl -1R, trans- -3- (2- methyI-oropvDs)-ring propionyl chloride are dissolved in 150g anhydrous tetrahydro furans, 25 DEG C by its
It is added drop-wise in previous solu.It is added dropwise, 120g water quenchings is added to go out reaction, filter, liquid separation, water layer is extracted with 3*100mL ethyl acetate
It takes.It is washed with water after merging organic phase to neutrality, depressurizes precipitation, receive 63g oily liquids, i.e. compound 1, yield 93%.
The synthesis of compound 2：
In the four round flask of the 1L with stirring, addition 124g compounds 1,124g acetic acid, 500g ethyl acetate,
Ozone is passed through at -10 DEG C.According to reaction process is controlled in gas-chromatography, treat that raw material conversion finishes, stop reaction.It is added in into system
100mL water, 60g zinc powders, finishes, and is to slowly warm up to be stirred at room temperature 8 hours.After temperature rising reflux two hours, filter, water phase 3*
50g ethyl acetate extracts, and merges organic phase, after being washed to neutrality, depressurizes precipitation, receives 98g oily liquids compound 2, yield
90%.
The synthesis of compound 3：
The compound 2 of 22g, the triphenylphosphine of 33.5g, the DMF of 100mL, nitrogen blowing are added in the four-hole boiling flask of 500mL
Afterwards, it is warming up to reflux.The trifluoro sodium chloroacetate of 25.5g is added portionwise at 150-160 DEG C, after adding, continues reflux 1 hour, drop
Temperature.200mL water is added in, with 3*100mL ethyl acetate aqueous layer extracteds.Merge organic phase, after depressurizing precipitation, 12.5g is made in rectifying
The compound 3 of oily, yield 51%.
The synthesis of compound 4 trans--the 3- of 2,2- dimethyl -1R- (2,2- difluoroethylenes base) cyclopropane-carboxylic acid：
It is added in the four round flask of 250mL, 10g compounds 3,50g1,2- dichloroethanes, 0.5g is to toluene sulphur
Acid is warming up to reflux, cools down after four hours, after washing, depressurizes precipitation, receives 6.7g compounds 4, yield 89%.
The synthesis of compound 5 trans--the 3- of 2,2- dimethyl -1R- (2,2- difluoroethylenes base) cyclopropane carboxylic acid acyl chlorides:
In the four-hole boiling flask of 250mL, the compound 4 of 6.7g is added in, the dichloroethanes of 40g adds in a few drop DMF, heating
To 50-60 DEG C, 5.4g thionyl chlorides are added dropwise, are added dropwise, keep the temperature 3 hours to get the trans- -3- (2,2- of 2,2- dimethyl -1R-
Difluoroethylene base) cyclopropane carboxylic acid acyl chlorides, which, which can not be handled, is directly used in subsequent synthesis.It can also negative pressure removing solvent
The higher acyl chlorides of purity is obtained as intermediate product for subsequently synthesis.
Embodiment 1：The compounds of this invention A1：The 2,3,5,6- ptfe benzyl trans- -3- of -2,2- dimethyl -1R- (2,2- bis-
It is fluoride-based) synthesis of cyclopropanecarboxylcompound
In the four-hole bottle of a 200ml, 2,3,5,6- tetrafluorobenzyl alcohol 10.0g (0.05mol), pyridine 5.0g are put into, it is molten
In 60ml toluene, throw and finish stirring, the trans- -3- of 2,2- dimethyl -1R- (2,2- difluoroethylene base) cyclopropane carboxylic acid is added dropwise at 0~5 DEG C
Acyl chlorides 9.73g (0.05mol), 20 DEG C of drop Bi Shengzhi react 4 hours.With 5% salt acid elutions of 400ml, then with 400ml 5%
NaHCO3 is washed, and separates oil reservoir 85 DEG C are heated under 10mmHg negative pressure and purify solvent toluene, obtains compound 2,3,5,6- tetra-
Trans--the 3- of luorobenzyl -2,2- dimethyl -1R- (2,2- difluoroethylene base) cyclopropanecarboxylcompound, column chromatography processing, receives weight
15.1g light brown yellow oily liquids, content 97.7%, yield 86%.The molecular formula of the compound：C15H12F6O2Molecular weight：
338.24 optically-actives [α]=- 7.66.Mass spectral molecular ion peak M=338.500000000 nuclear magnetic resonance spectroscopies (1H (ppm) CDCl3)：
6.57(m,1H)；5.34(s,2H)；3.90(d,1H)；1.51(t,1H)；1.09(d,1H)；1.11(s,6H).
Embodiment 2：Tetra- trans--the 3- of fluoro- 4- methylbenzyls -2,2- dimethyl -1R- of the compounds of this invention A2 2,3,5,6-
The synthesis of (2,2- difluoroethylenes base) cyclopropanecarboxylcompound
In the four-hole bottle of a 200ml, 2,3,5,6- tetrafluoros of input are to xylyl alcohol 10.7g (0.05mol), pyridine
5.0g is dissolved in 60ml toluene, throws and finishes stirring, the trans- -3- of 2,2- dimethyl -1R- (2,2- difluoroethylene base) are added dropwise at 0~5 DEG C
Cyclopropane carboxylic acid acyl chlorides 9.73g (0.05mol), 18 DEG C of drop Bi Shengzhi react 4 hours.With 5% salt acid elutions of 400ml, then use
400ml 5%NaHCO3 are washed, and separate oil reservoir 85 DEG C are heated under 10mmHg negative pressure and purify solvent toluene, obtain compound 2,
3,5, the 6- tetra- trans- -3- of fluoro- 4- methylbenzyls -2,2- dimethyl -1R- (2,2- difluoroethylene base) cyclopropanecarboxylcompounds, column layer
Analysis is handled, and receives weight 15.3g light brown yellow oily liquids, content 97.9%, yield 85%.The molecular formula of the compound：
C16H14F6O2Molecular weight：352.27 optically-actives [α]=- 7.69.Mass spectral molecular ion peak M=352.500000000 nuclear magnetic resonance spectroscopy (1H
(ppm)CDCl3)：5.34(s,2H)；3.90(d,1H)；2.45(s,3H)；1.51(t,1H)；1.11(s,6H)；1.07(d,
1H)；.
Testing example 1
By 0.05 gram of 2,3,5,6- ptfe benzyl -2,2- dimethyl -1R- trans- -3- (2,2- difluoroethylenes base) cyclopropane
Carboxylate (and the compounds of this invention A1) and 0.2 gram of Permethrin, 29.75 grams of D80 solvent naphthas (Exxon Mobil Corporation's product) add
Enter into inhalator jar, after loading onto aerosol valve to inhalator jar, 70 grams of third butane of propellant are pressed into inhalator jar, fully shake up aerosol
Content in tank.The aerosol of the present invention that the A1 of ester compounds containing chrysanthemum 0.05% has just been made in a transmission device is loaded onto to inhalator jar
Agent 1.Likewise, 0.05 gram of the compounds of this invention A2 and 2 is taken respectively, 3,5,6- ptfe benzyl -2,2- dimethyl -3- (2,2-
Difluoroethylene base) cyclopropanecarboxylcompound (the corresponding racemic modifications of the compounds of this invention A1), tetra- fluoro- 4- methyl benzyls of 2,3,5,6-
Base -2,2- dimethyl -3- (2,2- difluoroethylene base) cyclopropanecarboxylcompound (the corresponding racemic modifications of the compounds of this invention A2), is pressed
Above-mentioned steps operation preparation obtains aerosol 2 of the present invention, comparison aerosol 1 and comparison aerosol 2.
0.3 gram of dtetramethrin and 0.2 gram of Permethrin separately are taken, 29.5 grams of D80 solvent naphthas are added in inhalator jar, to gas
After the canned upper aerosol valve of mist, 70 grams of third butane of propellant are pressed into inhalator jar, fully shake up content in inhalator jar.To aerosol
Comparison aerosol 3, dtetramethrin content 0.3%. is prepared in a canned upper transmission device
Aerosol produced above with reference to GB13917.2-92 test the indoor harmacological effect of mosquito.Test worm is light color library
Mosquito, 2-3 days after emergence female mosquitos of not sucking blood.Using closed drum device.Detailed process is as follows：It will be put into cylinder, treat for examination insect
After test worm restores normal activity, the metered injection 1g medicaments from the insect aerosol tank of the present invention, extraction baffle makes examination after 1min
Worm and medicament contact, immediately timing, and start recording record the test worm number gone down at regular intervals, will all after 20min
It is transferred in clean dependent insect cage for test worm, checks dead test worm number afterwards for 24 hours.As a result it see the table below：
| Aerosol | Active ingredient | KT50(min) | The death rate (%) for 24 hours |
| Aerosol 1 of the present invention | The compounds of this invention A1 | 1.3 | 100 |
| Aerosol 2 of the present invention | The compounds of this invention A2 | 1.2 | 100 |
| Compare aerosol 1 | The corresponding raceme compounds of A1 | 1.7 | 100 |
| Compare aerosol 2 | The corresponding raceme compounds of A2 | 1.7 | 100 |
| Compare aerosol 3 | Dtetramethrin | 3.3 | 95 |
As can be seen that individual isomer compound of the present invention is approximately its racemic to the control effect of mosquito in aerosol
1.4 times of body compound, and it is apparently higher than currently used dtetramethrin.
Testing example 2
Respectively by the compounds of this invention A1, A2 and each 0.04 gram of eaphrenate, uniformly mixed with 7.96 grams of trimerization isobutylaldehydes
It is granular that ellipse is made after conjunction, obtains mothproof ball.With reference to Ministry of Textile Industry formulate " the mothproof Laboratory efficacy assay method of insect prevention ",
3 cylinders of test group, two cylinders of control group, not put drug, other are identical with test group for control 1, control 2 for drug test worm not
Put, in each cylinder placement hold 3 pieces of all woolen blank with culture dish, test group places one, the mothproof ball of above-mentioned preparation per cylinder, throws
5~7 instar larvae of attagenus piceus is put per 20, cylinder, the equal encapsulation process of cylinder mouth is stored into 1 DEG C of 26 scholar of temperature, relative humidity 6O scholar 5%,
Under dark experimental condition.Day by day test worm death toll is observed, calculates the death rate.Blank sheet is taken out after 14 days, with dry writing brush piecewise
Outwash removes excreta and sundries, each group all woolen blank is weighed one by one again, and observe each group all woolen blank extent of damage, pressed
Method seeks weightless protective rate in " the mothproof Laboratory efficacy assay method of insect prevention ".As a result such as following table：
| Mothproof ball active ingredient | Fabric weightlessness protective rate % | 14 days attagenus piceus death rate % | Fabric damage is classified |
| The compounds of this invention A1 | 92.5 | 70.0 | 0 |
| The compounds of this invention A2 | 92.2 | 55.0 | 0 |
| Eaphrenate | 90.2 | 20.0 | 0 |
| Blank control | 0.0 | 3 |
Testing example 3：Prevent brassicaceous vegetable (wild cabbage) diamondback moth raw test
Method：The compounds of this invention A1, the compounds of this invention A2 and control compounds gamma cyhalothrin are distinguished
With 7 gradient concentrations are diluted with the clear water of 0.5 ‰ Tween-80s respectively after acetone solution to 1% concentration, handled with clear water and make blank
Control, is measured using leaf dipping method, is taken out and is air-dried after diameter 2cm cabbage leaves are soaked into the liquid 10 seconds, is put in each culture dish
3 are put, if 3 repetitions, picking three ages diamondback moth larvae, picking 10 in each culture dish is then placed in 25 DEG C of illumination cultivations
In case, investigation survival borer population, the calculating death rate, the Mortality data by 7 concentration gradients calculate poison respectively after 48 hours
Power regression equation, finally obtains LC50.Measurement result such as the following table 1
Diamondback moth pharmacodynamic results
| Sample | Virulence regression equation | LC50(mg/l) |
| The compounds of this invention A1 | Y=2.6599X+1.4928 | 20.8246 |
| The compounds of this invention A2 | Y=2.4357X+2.1543 | 14.7350 |
| Gamma cyhalothrin | Y=1.9432X+2.1752 | 28.4259 |
Examples detailed above is technical concept and technical characterstic to illustrate the invention, can not limit the present invention's with this
Protection domain.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (10)
1. a kind of pyrethroid compound, which is characterized in that its structure is as shown in formula A：
R in formula is selected from H atom or methyl.
2. pyrethroid compound according to claim 1, it is characterised in that：When the R is H atom, the chemical combination
Object is 2,3,5,6- ptfe benzyl -2,2- dimethyl -1R- trans- -3- (2,2- difluoroethylenes base) cyclopropanecarboxylcompound.
3. pyrethroid compound according to claim 1, it is characterised in that：When the R is methyl, the compound
For 2,3,5,6- tetra- trans--the 3- of fluoro- 4- methylbenzyls -2,2- dimethyl -1R- (2,2- difluoroethylenes base) cyclopropanecarboxylcompound.
4. a kind of preparation method of claim 1-3 any one of them pyrethroid compounds, which is characterized in that including with
Lower step：2, the 2- trans- -3- of dimethyl -1R- (2,2- difluoroethylene base) cyclopropane-carboxylic acids or its corresponding acetyl halide compound,
In organic solvent, and 2,3,5,6- tetrafluorobenzyl alcohols or 2,3,5,6- tetrafluoros carry out esterification to xylyl alcohol, so as to obtain
The pyrethroid compound stated.
5. a kind of claim 1-3 any one of them pyrethroid compound is in prevention sanitary insect pest or agricultural pests side
The application in face.
6. application according to claim 5, which is characterized in that the sanitary insect pest is mosquito, fly, moth or blattaria.
7. application according to claim 5, which is characterized in that the agricultural pests are Tetranychus cinnabarinus or red spider.
8. application according to claim 5, which is characterized in that the pyrethroid compound is as active ingredient system
It is standby into conventional formulation for prevention sanitary insect pest or agricultural pests.
9. application according to claim 8, which is characterized in that the pyrethroid compound is as active ingredient system
During for into conventional formulation, conventional formulation includes the pyrethroid compound in itself or including the pyrethroid
Ester compounds and inert carrier.
10. application according to claim 9, which is characterized in that the conventional formulation includes the pyrethroid
When compound and inert carrier, the weight of pyrethroid compound accounts for the 0.001~95% of conventional formulation total weight.
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| CN201611245078.5A CN108250078A (en) | 2016-12-29 | 2016-12-29 | A kind of pyrethroid compound |
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| CN201611245078.5A CN108250078A (en) | 2016-12-29 | 2016-12-29 | A kind of pyrethroid compound |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776327A (en) * | 2019-02-27 | 2019-05-21 | 黄山学院 | Permethrin compound, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000046178A1 (en) * | 1999-02-05 | 2000-08-10 | Sumitomo Chemical Company, Limited | Ester compounds and pesticidal compositions |
| JP2007116967A (en) * | 2005-10-27 | 2007-05-17 | Dainippon Jochugiku Co Ltd | Chemical volatilization device |
| CN101580471A (en) * | 2008-05-16 | 2009-11-18 | 江苏扬农化工股份有限公司 | Pyrethroid compound, preparation method and application thereof |
-
2016
- 2016-12-29 CN CN201611245078.5A patent/CN108250078A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000046178A1 (en) * | 1999-02-05 | 2000-08-10 | Sumitomo Chemical Company, Limited | Ester compounds and pesticidal compositions |
| JP2007116967A (en) * | 2005-10-27 | 2007-05-17 | Dainippon Jochugiku Co Ltd | Chemical volatilization device |
| CN101580471A (en) * | 2008-05-16 | 2009-11-18 | 江苏扬农化工股份有限公司 | Pyrethroid compound, preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776327A (en) * | 2019-02-27 | 2019-05-21 | 黄山学院 | Permethrin compound, preparation method and application thereof |
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