CN101255147B - Spiromesifen derivative as well as synthesis and use thereof - Google Patents
Spiromesifen derivative as well as synthesis and use thereof Download PDFInfo
- Publication number
- CN101255147B CN101255147B CN2008100603249A CN200810060324A CN101255147B CN 101255147 B CN101255147 B CN 101255147B CN 2008100603249 A CN2008100603249 A CN 2008100603249A CN 200810060324 A CN200810060324 A CN 200810060324A CN 101255147 B CN101255147 B CN 101255147B
- Authority
- CN
- China
- Prior art keywords
- spiromesifen
- derivative
- mite
- spirodiclofen
- derivate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical class CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 title claims description 20
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 238000010189 synthetic method Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 8
- 239000005664 Spirodiclofen Substances 0.000 abstract description 5
- DTDSAWVUFPGDMX-UHFFFAOYSA-N spirodiclofen Chemical compound CCC(C)(C)C(=O)OC1=C(C=2C(=CC(Cl)=CC=2)Cl)C(=O)OC11CCCCC1 DTDSAWVUFPGDMX-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- VNTCVNLNEOVBEE-UHFFFAOYSA-N 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carbonyl chloride Chemical compound CC(C)=CC1C(C(Cl)=O)C1(C)C VNTCVNLNEOVBEE-UHFFFAOYSA-N 0.000 abstract 1
- 244000045947 parasite Species 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 241000723353 Chrysanthemum Species 0.000 description 7
- 235000007516 Chrysanthemum Nutrition 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 241000488583 Panonychus ulmi Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000642 acaricide Substances 0.000 description 6
- 150000001263 acyl chlorides Chemical class 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000006071 cream Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 102000002322 Egg Proteins Human genes 0.000 description 4
- 108010000912 Egg Proteins Proteins 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 4
- 150000001335 aliphatic alkanes Chemical group 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 210000004681 ovum Anatomy 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241000409991 Mythimna separata Species 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000014347 soups Nutrition 0.000 description 3
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- 238000007445 Chromatographic isolation Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004166 bioassay Methods 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 238000011097 chromatography purification Methods 0.000 description 2
- 230000000857 drug effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 2
- -1 tertiary amine compounds Chemical class 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 241001425390 Aphis fabae Species 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- 241001182720 Cacopsylla pyrisuga Species 0.000 description 1
- 235000002566 Capsicum Nutrition 0.000 description 1
- 240000008574 Capsicum frutescens Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001414720 Cicadellidae Species 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000368289 Lepidosaphes ulmi Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000819999 Nymphes Species 0.000 description 1
- 241001012098 Omiodes indicata Species 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 241001674048 Phthiraptera Species 0.000 description 1
- 241000952063 Polyphagotarsonemus latus Species 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 239000005665 Spiromesifen Substances 0.000 description 1
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001390 capsicum minimum Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000004132 lipogenesis Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000003129 miticidal effect Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a spirodiclofen derivate with the structure general formula shown in the drawing I. The invention also discloses a synthetic method of the spirodiclofen derivate, comprising: reacting the compound with the structural formula shown in the drawing II with the chrysanthemoyl chloride with the structural formula like R-Cl at 0-30 DEG C under the existing condition of acid binding agent and non-proton organic solvent, separating the obtained reaction solution to obtain the spirodiclofen derivate. The spirodiclofen derivate can be used for destroying parasites and killing mite.
Description
Technical field
The invention belongs to pesticide field, related to a series of new Spiromesifen derivatives, the invention still further relates to the mensuration of the activeconstituents of this series compound the prevention effect of harmful organism.
Background technology
Spiral shell mite ester (formula III compound) also claims spirodiclofen, is first keto-enol formula class desinsection/miticide of Beyer Co., Ltd's exploitation, is the effective constituent of Pesticidal products " mite danger ".Mite danger is a kind of brand-new, efficient non-internal-absorting foliar treatment miticide, different mite classes to various crop all have good preventive effect and outstanding long-lasting, its can kill ovum can kill again the children (if) mite, be particularly suitable for preventing and treating the pest mite class that existing miticide is produced resistance.The mechanism of action of spiral shell mite ester is to suppress the intravital lipogenesis of pest mite.Do not have cross resistance between it and the existing miticide, be applicable to that control produces the pest mite class of resistance to existing miticide.Mite danger all has fine preventive effect to red spider, yellow spider, Xiu Pi lice, yellow tea mite, carmine spider mite and Tetranychus urticae etc., and the mite evil that can be used for solanaceous crops such as fruit tree such as citrus, grape and eggplant, capsicum, tomato is administered.In addition, mite danger has the well double effect of controlling to insects such as pear sucker, oystershell scale and leafhopper classes.Mite danger all has good contact toxicity to full growth period of pest mite (comprise ovum, young mite, if mite, female one-tenth mite etc.), and is especially more outstanding to the contact toxicity of ovum, to people and animals and crop safety, low toxicity, is suitable for nuisanceless production.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of Spiromesifen derivative with better desinsection, miticidal effect and preparation method thereof.
In order to solve the problems of the technologies described above, the invention provides a kind of Spiromesifen derivative, its general structure is:
Wherein R is:
The present invention also provides the synthetic method of above-mentioned Spiromesifen derivative: under the situation of acid binding agent and non-proton organic solvent existence, make structural formula be at 0～30 ℃
Compound and structural formula chrysanthemum acyl chloride reaction 0.4～1h of being R-Cl, wherein R is:
The gained reaction solution is separated promptly; The mol ratio of compound, chrysanthemum acyl chlorides and acid binding agent is 1: 1～2: 2～6.
Improvement as the synthetic method of Spiromesifen derivative of the present invention: non-proton organic solvent is alkanes, ethers, arene, alkane substitute class or substituted aroma hydro carbons; Described acid binding agent is the tertiary amine compounds.Alkanes is normal hexane or hexanaphthene, and ethers is an ether, and arene is benzene or toluene, and the alkane substitute class is methylene dichloride or 1, the 2-ethylene dichloride; The tertiary amine compounds is triethylamine or pyridine etc.
Further improvement as the synthetic method of Spiromesifen derivative of the present invention: the chrysanthemum acyl chlorides adds in the mode that drips, and the temperature of dropping is 0～5 ℃.
As the further improvement of the synthetic method of Spiromesifen derivative of the present invention, isolating method is: reaction solution is carried out recrystallization.Solvent for use is C in the recrystallization
1-C
4In any primary alcohol.
The present invention also provides the purposes of above-mentioned Spiromesifen derivative: be used for desinsection or kill mite.
The objective of the invention is from 3-(2,4 dichloro benzene base)-2-oxo-1-oxaspiro [4.5]-last of the ten Heavenly stems-3-alkene 4-alcohol and the reaction of different chrysanthemum acyl group, thereby prepare the derivative of serial spiral shell mite ester; Therefrom obtain to have the compound of better prevention harmful organism with expectation.
The synthetic method of Spiromesifen derivative of the present invention can be illustrated with following equation:
In synthetic method of the present invention, the compound of formula II is report and synthetic in US6436988.
For the convenience of explaining, the R among the R-Cl is made following mark:
R：
The above-mentioned synthetic serial new compound that obtains is carried out indoor bioassay with the mythimna separata and the red spider at two initial stages in age respectively, and under 600ppm, all compounds all show good biological activity.
The invention has the advantages that: synthesized the new compound that is different from formula III that series is not appeared in the newspapers, and biological activity preferably arranged, specifically to the activity of acarid under same dose, some new compound is active more taller than Spiromesifen.
Spiromesifen derivative of the present invention, as follows at the actual usage and the consumption in field:
With structural formula is that the compound 24g of 3a and agricultural newborn 500#4g, agricultural newborn 602#5 gram, soil temperature 20#2 gram, height ooze 1g, is made into the cream preparation of 24% (w/w) after dimethylbenzene 64g mixes.
1, when being used for killing mite:
1), application process: even spraying, when medicament was converted water spray, it was even to spray as far as possible, guarantees that soup sprays application to blade tow sides and fruit surface, brings into play its drug effect to greatest extent.
2), time of application: suggestion is caused harm the evil mite and is used early stage.
3), application program: when the harm of evil mite reaches index for control (every leaf worm ovum number reaches 10 or every leaf nymph 3-4 head); use 3a cream preparation 4000-5000 doubly to dilute back (converting water 800-1000 jin for 100 milliliters every bottle) even spraying, every mu of consumption is 35～50mL cream preparation.
2, when being used for desinsection:
1), application process: even spraying, when medicament was converted water spray, it was even to spray as far as possible, guarantees that soup sprays application to blade tow sides and fruit surface, brings into play its drug effect to greatest extent.
2), time of application: suggestion is caused harm insect and is used early stage.
3), application program: when the aphid that is used to prevent and treat on the vegetables, with above-mentioned cream preparation and water according to 1: 4000～5000 dilution proportion after, contain the phase spraying of sending out wingless aphid and handle, every mu of consumption is 35～50mL cream preparation.
Embodiment
The synthetic method of embodiment 1, a kind of Spiromesifen derivative, its reaction formula is:
Concrete reaction process is as follows:
In reaction flask, add 5.0g (16.0mmol) 3-(2 under the ice-water bath, the 4-dichlorophenyl)-2-oxo-1-oxaspiro [4.5]-last of the ten Heavenly stems-3-alkene-4-alcohol (structural formula is II), 6.0g (60.0mmol) triethylamine and 80mL methylene dichloride, drip 3.6g (19.3mmol) dimethyl chrysanthemum acyl chlorides in 0～5 ℃ again, after dropwising, (0～30 ℃) stirring reaction 0.5h under the room temperature.Reaction solution is used saturated NaHCO again with 1% salt acid elution three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying, concentrate the 7.8g solid product, through ethyl alcohol recrystallization, after the filtering separation 6.9g product 3a (being the 3a in the table 1), Y=93.4%.
1H-NMR(400MHz，CDCl
3，δppm)：7.42～7.22(3H，m，ph-H
3)，4.91～4.89(1H，d，Me
2＝CH-)，2.01～2.0(1H，m，Me
2＝CH-CH)，1.83～1.73(10H，m，Cyclohexane-H
10)，1.66～1.60(6H，s，Me
2＝C-)，1.54～1.53(2H，d，O＝C-CH)，1.18～1.10(6H，s，Me
2-C-)。
The synthetic method of embodiment 2, a kind of Spiromesifen derivative, its reaction formula is:
Concrete reaction process is as follows:
In reaction flask, add 5.0g (16.0mmol) 3-(2 under the ice-water bath,-dichlorophenyl)-2-oxo-1-oxaspiro [4.5]-last of the ten Heavenly stems-3-alkene 4-alcohol (structural formula is II) and 6.0g (60.0mmol) triethylamine, with the 80mL methylene dichloride, drip 4.6g (20mmol) 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine in 0～5 ℃ again, after dropwising, (0～30 ℃) stirring reaction 0.8h under the room temperature.Reaction solution is used saturated NaHCO again with 1% salt acid elution three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying, concentrate the 8.0g solid product, through ethyl alcohol recrystallization, after the filtering separation 7.1g product (being the 3d in the table 1), Y=95.5%.
1H-NMR(δppm)：7.27～7.04(7H，m，ph-H
7)，3.27～3.25(1H，d，Ph-CH-)，2.25～2.19(1H，m，Ph-CH-CH)，1.74～1.60(10H，m，Cyclohexane-H
10)，0.95～0.94(3H，d，Me-C-)，0.69～0.67(3H，d，Me-C-)。
The synthetic method of embodiment 3, a kind of Spiromesifen derivative, its reaction formula is:
Concrete reaction process is as follows:
In reaction flask, add 5.0g (16.0mmol) 3-(2 under the ice-water bath, the 4-dichlorophenyl)-2-oxo-1-oxaspiro [4.5]-last of the ten Heavenly stems-3-alkene 4-alcohol (structural formula is II) and 6.0g (60.0mmol) triethylamine, with the 80mL methylene dichloride, drip 4.8g (20mmol) chrysanthemum acyl chlorides in 0～5 ℃ again, after dropwising, stirring reaction 0.5h under the room temperature.Reaction solution is used saturated NaHCO again with 1% salt acid elution three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying, concentrate the 8.5g solid product, behind column chromatographic isolation and purification 7.0g product (being the 3g in the table 1), Y=91.9%.
1H-NMR(δppm)：7.41～7.30(3H，m，ph-H
3)，6.45～6.43(1H，d，Cl(CF3)＝CH-)，2.36～2.34(1H，m，Cl(CF3)＝CH-CH)，2.17～2.15(1H，d，O＝C-CH)，1.83～1.75(10H，m，Cyclohexane-H
10)，1.35～1.10(6H，s，Me
2-C-)。
The synthetic method of embodiment 4, a kind of Spiromesifen derivative, its reaction formula is:
Concrete reaction process is as follows:
In reaction flask, add 5.0g (16.0mmol) 3-(2 under the ice-water bath, the 4-dichlorophenyl)-2-oxo-1-oxaspiro [4.5]-last of the ten Heavenly stems-3-alkene 4-alcohol (structural formula is II) and 80.0mmol pyridine, with 80mL toluene, again in 0～5 ℃ of dibromo chrysanthemum acyl chlorides that drips 4.1g (20mmol), after dropwising, stirring reaction 0.5h under the room temperature.Reaction solution is used saturated NaHCO again with 1% salt acid elution three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying, concentrate the 9.2g solid product, behind column chromatographic isolation and purification 7.8g product (being the 3i in the table 1), Y=90.1%.
1H-NMR(CDCl
3，δppm)：7.42～7.31(3H，m，ph-H
3)，6.29～6.27(1H，d，Br
2＝CH-)，2.17～2.13(1H，m，Br
2＝CH-CH)，2.04～2.02(1H，d，O＝C-CH)，1.81～1.79(10H，m，Cyclohexane-H
10)，1.29(3H，s，Me-C-)，1.06(3H，s，Me-C-)。
Embodiment 5,
Adopt pickling process, after will dissolving with acetone solvent for the examination bulk drug, be diluted to the aqueous solution of 600mg/L, the examination worm dipping of getting in the soup of every kind of different Spiromesifen derivative about 60 took out after 30 seconds, was placed on the filter paper and dried naturally.Then, putting the glass that bright leaf is housed respectively into supports in the scolite, be placed on temperature and be 24 ℃, atmospheric moisture and be 60% about the greenhouse, use the red spider larva (representative acarid) at two initial stages in age, the black bean aphid mythimna separata at two initial stages in age to carry out indoor bioassay respectively to 10 new compounds of synthetic, the mortality ratio of mythimna separata behind red spider and the 48h behind the 96h of observation statistics respectively.General sieve the results are shown in Table 1, and compound 3a, 3b, 3c, 3e, 3g, 3h have good activity to red spider.
The general sieve measurement result of table 1 compound pesticide and miticide actility
| ck | 0 | - | - |
| 3a | 600 | 100 | 100 |
| 3b | 600 | 100 | 66.7 |
| 3c | 600 | 100 | 66.7 |
| 3d | 600 | 66.7 | 36.3 |
| 3e | 600 | 100 | 64.7 |
| 3f | 600 | 33.3 | 67 |
| 3g | 600 | 100 | 28.5 |
| 3h | 600 | 100 | 66.7 |
| 3i | 600 | 7.60 | 33 |
| 3j | 600 | 66.7 | 20 |
| II | 600 | 58.6 | 33.3 |
| III | 600 | 96 | 100 |
Annotate: II represents the compound of formula II, and III represents the compound (being spiral shell mite ester) of formula III.
According to the content of above table 1, we can learn: under same dose, compound 3a, 3b, 3c, 3e, 3g and the 3h of gained of the present invention will be higher than existing spiral shell mite ester to the activity of red spider.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (2)
1. Spiromesifen derivative is characterized in that general structure is:
Wherein R is:
2. as requiring the purposes of 1 described Spiromesifen derivative, it is characterized in that: be used for desinsection or kill mite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100603249A CN101255147B (en) | 2008-04-03 | 2008-04-03 | Spiromesifen derivative as well as synthesis and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100603249A CN101255147B (en) | 2008-04-03 | 2008-04-03 | Spiromesifen derivative as well as synthesis and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101255147A CN101255147A (en) | 2008-09-03 |
| CN101255147B true CN101255147B (en) | 2011-05-04 |
Family
ID=39890309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100603249A Expired - Fee Related CN101255147B (en) | 2008-04-03 | 2008-04-03 | Spiromesifen derivative as well as synthesis and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101255147B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928272B (en) * | 2010-06-12 | 2013-05-22 | 湖南化工研究院 | 3-o-methylphenyl-2-oxo-1-oxaspiro[4,5]-decyl-3-alkene-4-ol derivative |
| CN102060818B (en) * | 2011-01-07 | 2012-02-01 | 青岛科技大学 | Novel spirodiclofen compound and preparation method and application thereof |
| CN112745286B (en) * | 2020-12-30 | 2023-01-24 | 浙江宇龙药业有限公司 | Preparation method of spirodiclofen diester derivative |
-
2008
- 2008-04-03 CN CN2008100603249A patent/CN101255147B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101255147A (en) | 2008-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2547534C2 (en) | Cyclopropanecarboxylic acid esters, process for their preparation and their use | |
| DE2826864C2 (en) | ||
| DE2513732C2 (en) | ||
| PL112140B1 (en) | Insecticide | |
| UA119536C2 (en) | 4-amino-6-(heterocyclic)picolinates and 6-amino-2-(heterocyclic)pyrimidine-4-carboxylates and their use as herbicides | |
| DE3534948A1 (en) | FUNGICIDES AND GROWTH REGULATORY AGENTS | |
| EP0243313A1 (en) | Acyl-cyclohexane diones and their oxime ethers exhibiting a herbicidal and plant growth activity | |
| CN103214461B (en) | Quinoline derivative and application thereof | |
| CN111393429A (en) | Isothiazole oxadiazole biphenyl amide derivatives and preparation method and application thereof | |
| DE3919348A1 (en) | MICROBICIDAL AGENTS | |
| CN101255147B (en) | Spiromesifen derivative as well as synthesis and use thereof | |
| EP0063101A1 (en) | Nitroaryl-alkyl-sulfone derivatives as gametocides | |
| DD149935A5 (en) | PROCESS FOR THE PREPARATION OF RACEMENS OR OPTICALLY ACTIVE 2- (PROPARGYLOXYIMINO) -1,7,7-TRIMETHYLBICYCLO (2,2,1) HEPTANE | |
| DE2647366A1 (en) | SUBSTITUTED AYLAC ACID ESTERS, PROCESS FOR THEIR MANUFACTURING, AND INSECTICIDES AND ACARICIDAL AGENTS | |
| DE19934952A1 (en) | New cyclopenta-benzofuran derivatives, used as pesticides, especially insecticides and acaricides for plant protection | |
| DD295160A5 (en) | MICROBICIDE MEDIUM | |
| DE2647368A1 (en) | Phenoxybenzyl pyrrole-(1)-acetate derivs. - with insecticidal and acaricidal activity | |
| DE2114367A1 (en) | Organic tin compounds and processes for their production | |
| CN101250174B (en) | Spiromesifen derivative as well as synthesis and use thereof | |
| DE1618968C2 (en) | ||
| EP0065483A1 (en) | Acyl aniline and acylnaphthyl amine microbicides, processes for preparing them and their use | |
| CH663021A5 (en) | THIOCYANOPYRIMIDINE DERIVATIVE, METHOD FOR PRODUCING THE SAME AND THE SAME AGRICULTURAL AND GARDEN ECONOMIC Fungicide Containing Effective Ingredients. | |
| JPS6254281B2 (en) | ||
| CN110183434B (en) | Oxadiazole compound and preparation method and application thereof | |
| DE3405417A1 (en) | SUBSTITUTED OXIRANS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110504 Termination date: 20140403 |