CN114605386A - Fluorine-containing pyrimidine thioether aromatic ester insecticide and acaricide - Google Patents
Fluorine-containing pyrimidine thioether aromatic ester insecticide and acaricide Download PDFInfo
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- CN114605386A CN114605386A CN202210373896.2A CN202210373896A CN114605386A CN 114605386 A CN114605386 A CN 114605386A CN 202210373896 A CN202210373896 A CN 202210373896A CN 114605386 A CN114605386 A CN 114605386A
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- acaricide
- fluorine
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- aromatic ester
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- 230000000895 acaricidal effect Effects 0.000 title claims abstract description 19
- 239000000642 acaricide Substances 0.000 title claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 7
- 239000011737 fluorine Substances 0.000 title claims abstract description 7
- 239000002917 insecticide Substances 0.000 title claims description 10
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 title claims description 4
- 150000003568 thioethers Chemical class 0.000 title claims description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 14
- 241000238876 Acari Species 0.000 claims abstract description 11
- -1 pyrimidine thioether aromatic ester compound Chemical class 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000000749 insecticidal effect Effects 0.000 claims description 4
- WAVYAFBQOXCGSZ-UHFFFAOYSA-N 2-fluoropyrimidine Chemical compound FC1=NC=CC=N1 WAVYAFBQOXCGSZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 230000002147 killing effect Effects 0.000 abstract description 12
- 239000000575 pesticide Substances 0.000 abstract description 8
- 241000238631 Hexapoda Species 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003814 drug Substances 0.000 description 9
- MXWAGQASUDSFBG-RVDMUPIBSA-N fluacrypyrim Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1COC1=CC(C(F)(F)F)=NC(OC(C)C)=N1 MXWAGQASUDSFBG-RVDMUPIBSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 241000500437 Plutella xylostella Species 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229940125890 compound Ia Drugs 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000000902 placebo Substances 0.000 description 4
- 229940068196 placebo Drugs 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- WPALTCMYPARVNV-UHFFFAOYSA-N tolfenpyrad Chemical compound CCC1=NN(C)C(C(=O)NCC=2C=CC(OC=3C=CC(C)=CC=3)=CC=2)=C1Cl WPALTCMYPARVNV-UHFFFAOYSA-N 0.000 description 4
- OIXRLPWNVSSGHR-UHFFFAOYSA-N 2-butylsulfanyl-6-(trifluoromethyl)-1h-pyrimidin-4-one Chemical compound CCCCSC1=NC(=O)C=C(C(F)(F)F)N1 OIXRLPWNVSSGHR-UHFFFAOYSA-N 0.000 description 3
- 241000500441 Plutellidae Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SDZUYDOXBXHDCE-UHFFFAOYSA-N 2-(4-fluorophenoxy)pyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=C1OC1=CC=C(F)C=C1 SDZUYDOXBXHDCE-UHFFFAOYSA-N 0.000 description 2
- YZAOETRYQWFEOY-UHFFFAOYSA-N 2-sulfanylidene-6-(trifluoromethyl)-1h-pyrimidin-4-one Chemical compound FC(F)(F)C1=CC(=O)NC(=S)N1 YZAOETRYQWFEOY-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- 240000007124 Brassica oleracea Species 0.000 description 2
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 2
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 2
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 2
- 244000141359 Malus pumila Species 0.000 description 2
- 241000488583 Panonychus ulmi Species 0.000 description 2
- 240000006677 Vicia faba Species 0.000 description 2
- 235000010749 Vicia faba Nutrition 0.000 description 2
- 235000002098 Vicia faba var. major Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- GJUABKCEXOMRPQ-UHFFFAOYSA-N 1-[(2,5-dimethoxyphenyl)diazenyl]naphthalen-2-ol Chemical compound COC1=CC=C(OC)C(N=NC=2C3=CC=CC=C3C=CC=2O)=C1 GJUABKCEXOMRPQ-UHFFFAOYSA-N 0.000 description 1
- BQDJLAWUTBCDHK-UHFFFAOYSA-N 2-(trifluoromethyl)pyrimidine Chemical group FC(F)(F)C1=NC=CC=N1 BQDJLAWUTBCDHK-UHFFFAOYSA-N 0.000 description 1
- JAUPUQRPBNDMDT-UHFFFAOYSA-N 2-chloropyridine-3-carbonitrile Chemical compound ClC1=NC=CC=C1C#N JAUPUQRPBNDMDT-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000500439 Plutella Species 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- AAHZCIWUDPKSJP-UHFFFAOYSA-N methyl 2-(chloromethyl)benzoate Chemical compound COC(=O)C1=CC=CC=C1CCl AAHZCIWUDPKSJP-UHFFFAOYSA-N 0.000 description 1
- 230000003129 miticidal effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000012865 response to insecticide Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 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 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/56—One oxygen atom and one sulfur atom
Abstract
The invention provides a fluorine-containing pyrimidine thioether aromatic ester compound, which has a structure shown as a general formula I:
wherein R1 is: CH (CH)3CH2CH2CH2‑,CF3CH2-; r2 is:
Description
The invention belongs to the field of insecticides and acaricides in pesticides, and relates to a fluorine-containing pyrimidine thioether aromatic ester insecticide and acaricide and application thereof to prevention and control of pests and mites in agriculture or forestry.
Background agricultural pest and mite harm the growth of crops, resulting in reduced yield and reduced quality. At present, the prevention and control of pests and mites mainly depend on chemical pesticides, and due to the fact that a large number of insecticides and acaricides are frequently used, the pests and mites have serious drug resistance to the insecticides and acaricides, so that the pesticide consumption is increased, the prevention effect is reduced, the lasting period is shortened, pesticide residues are increased, and the like. The development and application of new insecticidal and acaricidal agents with different action mechanisms are effective means for solving pest resistance. The fluacrypyrim is a fluoropyrimidine acrylate acaricide researched and developed by Pasteur company and Japanese Caoda company, is mainly used for preventing and controlling fruit trees, and particularly has excellent biological performance in preventing and controlling various mites such as apple red spider, citrus red spider and the like in fruit trees such as apples, oranges, pears and the like. Although the compounds (I) of the present invention are structurally similar to fluacrypyrim, in that they contain a trifluoromethylpyrimidine ring, the compounds of formula I as defined in the present invention and their use as agricultural insecticides and acaricides have not been disclosed in the prior art.
The invention aims to provide an insecticide and acaricide which has novel structure, simple and convenient synthesis method, safety and high efficiency, and can be used for preventing and controlling pest mites of agricultural or forestry pests.
The technical scheme of the invention is as follows:
the fluorine-containing pyrimidine thioether aromatic ester compound has a structure shown in a general formula I:
the compounds of the general formula I according to the invention can be prepared by the following method:
wherein R1 and R2 are as above, and X is Cl or Br.
The compound of formula II and the compound of formula III are esterified (or substituted) in ethyl acetate (or DMF) by taking triethylamine (or potassium carbonate) as a catalyst at room temperature or under heating to prepare the compound of formula I. The concrete preparation method is shown in the synthesis example of the invention. Table 1 shows the structures and appearances of the compounds of formula I.
TABLE 1 Structure and appearance of compounds of general formula I
The invention has the advantages and positive effects that:
the compound (general formula I) is used as an agricultural insecticide and acaricide, and has the advantages of novel structure, simple and convenient preparation and dual control of insects and mites. The compound has good effect of inhibiting and killing diamondback moth and tetranychus cinnabarinus, and can achieve the excellent effect of controlling pests and mites in agriculture and forestry. Compared with the commercial pesticide tolfenpyrad, the killing effect of Ib and IE on the diamondback moth is close to that of tolfenpyrad. Compared with the commercial miticide fluacrypyrim, the killing rate of the acaricidal composition to diamondback moths is obviously higher than that of fluacrypyrim, wherein the killing rate of Ig to tetranychus cinnabarinus is close to that of fluacrypyrim. The compound is a fluorine-containing nitrogen heterocyclic compound, has the characteristics of high biological activity, low toxicity to beneficial organisms, easy degradation and good environmental compatibility, is particularly suitable for the treatment of the pesticide-resistant agricultural pests and mites which commonly exist at present, and has good development and application prospects as a new variety of pesticides with pesticide and mite killing functions.
The compound of the invention is used for preventing and controlling agricultural pests or mites, can be used alone, and can also be used in combination with other active substances, so as to improve the comprehensive performance of the product.
The invention also comprises a disinsection and acaricidal composition which takes the compound shown in the general formula I as an active component, wherein the weight percentage of the active component in the composition is 1-99%. The insecticidal and acaricidal composition also comprises an agriculturally or forestry acceptable carrier.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
Detailed Description
The following synthetic examples, biological test results, are provided to further illustrate the invention, but are not meant to limit the invention.
Synthesis examples
Example 1, preparation of compound ia:
(1) synthesis of intermediate compounds of formula ii:
in a 250mL three-mouth reaction bottle, 19.62g (0.10mol) of 2-mercapto-4-hydroxy-6-trifluoromethylpyrimidine and 16.59g (0.12mol) of potassium carbonate are added into 50mL of DMF, stirred at room temperature for 10min, 15.07g (0.11mol) of n-bromobutane is added dropwise, after the dropwise addition is finished, the reaction is carried out at room temperature for 3h, TLC is used for monitoring the reaction to be complete, the reaction solution is poured into 150mL of water, and hydrochloric acid is added dropwise under stirring to adjust to neutrality, so that solid is separated out. Suction filtration, washing, filter cake collection and drying, compound 2- (n-butylsulfanyl) -4-hydroxy-6- (trifluoromethyl) pyrimidine, yield 87%.
In a similar manner, 2-mercapto-4-hydroxy-6-trifluoromethylpyrimidine was reacted with 1-iodo-2-trifluoroethane to give the compound 2- ((2,2, 2-trifluoroethyl) thio) -4-hydroxy-6- (trifluoromethyl) pyrimidine as a pale yellow oil in 92% yield.
(2) Synthesis of intermediate 2- (4-fluorophenoxy) nicotinoyl chloride
1) 13.86g (0.1moL) of 2-chloronicotinonitrile, 11.21g (0.1moL) of para-fluorophenol and 16.59g (0.12moL) of potassium carbonate are added into a 250mL three-neck flask, then 100mL of DMF is added as a reaction solvent, stirring is carried out, after 3 hours of reflux reaction, TLC is used for monitoring the reaction completion, 150mL of water is added, white solid is separated out, and the intermediate 2- (4-fluorophenoxy) nicotinonitrile is obtained with the yield of 92%.
2) In a 250mL three-necked flask, the 2- (4-fluorophenoxy) nicotinonitrile obtained in the above step and potassium hydroxide (0.1mol) were added, 100mL of water was added as a reaction solvent, and the mixture was stirred, and the reaction temperature was raised to reflux, and the reaction was completed as monitored by TLC. Reducing the reaction temperature, adding hydrochloric acid to adjust to weak acidity, separating out solid, performing suction filtration and drying to obtain a crude product of 2- (4-fluorophenoxy) nicotinic acid with the yield of 62%.
3) In a 250mL single-neck round bottom flask, 23.3g (0.1mol) of 2- (4-fluorophenoxy) nicotinic acid and 17.85g (0.15mol) of thionyl chloride are added, 80mL of toluene is added as a solvent, the reaction solution is heated to reflux, the reaction is carried out for 4h, TLC is used for monitoring the reaction completion, and the toluene and the residual thionyl chloride are removed by reduced pressure distillation, so that 2- (4-fluorophenoxy) nicotinoyl chloride is obtained as a white solid with the yield of 98%.
(3) Synthesis of compound ia:
2.52g (10.0mmol) of 2- (n-butylthio) -4-hydroxy-6- (trifluoromethyl) pyrimidine and 1.21g (12.0mmol) of triethylamine are added into a 100mL three-neck flask, then 20mL of ethyl acetate is added as a reaction solvent, stirring is carried out at room temperature for 0.5h, 2.64g (10.5mmol) of 2- (4-fluorophenoxy) nicotinoyl chloride is added in batches, the reaction temperature is controlled at room temperature, the reaction is carried out for 3-5h, and the completion of the reaction is monitored by TLC. After cooling, 60mL of water was added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 30mL), the organic layer was washed with brine (2 × 20mL) and dried over anhydrous sodium sulfate, and the ethyl acetate was removed by distillation under reduced pressure, and the crude product was separated by column chromatography (V (ethyl acetate): V (petroleum ether): 1:10) to give the objective compound ia. A colorless oil in 67% yield.
Example 2, preparation of compound ic:
25.2g (0.1mol) of 2- (n-butylthio) -4-hydroxy-6- (trifluoromethyl) pyrimidine and 12.1g (0.12mol) of triethylamine are added into a 250mL three-neck flask, then 200mL of ethyl acetate is added as a reaction solvent, the mixture is stirred at room temperature for 0.5h, 20.0g (0.105mol) of p-toluenesulfonyl chloride is added in portions, the reaction temperature is controlled at room temperature, the reaction is carried out for 3-5h, and the completion of the reaction is monitored by TLC. After cooling, 100mL of water was added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 30mL), and the remaining organic layer was washed with brine (2 × 20mL), dried over anhydrous sodium sulfate, and distilled under reduced pressure to remove ethyl acetate, and the crude product was separated by column chromatography (V (ethyl acetate): V (petroleum ether): 1:10) to give the objective compound ic. Colorless oil, yield 65%.
Example 3 preparation of compound ig:
in a 100mL three-necked flask, 2.78g (10.0mmol) of 2- ((2,2, 2-trifluoroethyl) thio) -4-hydroxy-6- (trifluoromethyl) pyrimidine and 1.66g (12.0mmol) of potassium carbonate were added, 20mL of DMF was added as a reaction solvent, and the mixture was stirred at room temperature for 0.5h, 1.94g (10.5mmol) of methyl 2-chloromethylbenzoate was added in portions, and the reaction was continued for 3 to 5h by warming to 85 ℃ and monitoring the completion of the reaction by TLC. After cooling to room temperature, 60mL of water was added to the reaction mixture, extraction was performed with ethyl acetate (3 × 30mL), the organic layer was dried over anhydrous sodium sulfate, the remaining ethyl acetate was removed by distillation under the reduced pressure, and the crude product was purified by column chromatography (V (ethyl acetate): V (petroleum ether) ═ 1:10) to give the objective compound ig. White solid, yield 71%.
The synthesis of compounds Ib, Id, ie, if is analogous to Ia.
The nuclear magnetic data of the compounds of the general formula I of the invention are as follows:
a compound Ia:1H NMR(500MHz,Chloroform-d)δ8.52(dd,J＝7.7,2.0Hz,1H),8.39(dd,J＝4.9,2.0Hz,1H),7.31(s,1H),7.21–7.07(m,5H),3.21(t,J＝7.4Hz,2H),1.81–1.71(m,2H),1.49(dt,J＝14.6,7.4Hz,2H),0.97(t,J＝7.4Hz,3H).
a compound Ib:1H NMR(500MHz,Chloroform-d)δ8.13(dd,J＝8.7,2.0Hz,2H),7.59–7.54(m,2H),3.20(t,J＝7.4Hz,2H),1.80–1.71(m,2H),1.49(q,J＝7.4Hz,2H),1.39(s,9H),0.97(t,J＝7.4Hz,3H).
a compound ic:1H NMR(500MHz,Chloroform-d)δ8.01–7.91(m,2H),7.45–7.38(m,2H),6.92(s,1H),3.08(t,J＝7.4Hz,2H),2.49(s,3H),1.74–1.64(m,2H),1.46(h,J＝7.4Hz,2H),0.95(t,J＝7.4Hz,3H).
a compound id:1H NMR(500MHz,Chloroform-d)δ8.51(d,J＝7.7Hz,1H),8.39(d,J＝5.0Hz,1H),7.44(s,1H),7.18(dd,J＝7.8,5.0Hz,1H),7.14(t,J＝4.6Hz,2H),7.11(t,J＝8.5Hz,2H),3.98(q,J＝9.6Hz,2H).
a compound ie:1H NMR(500MHz,Chloroform-d)δ8.14(d,J＝8.5Hz,2H),7.58(d,J＝8.5Hz,2H),7.42(s,1H),4.01(q,J＝9.7Hz,2H),1.39(s,9H).
a compound if:1H NMR(500MHz,Chloroform-d)δ8.07(d,J＝7.4Hz,1H),7.87(d,J＝7.6Hz,1H),7.80–7.71(m,2H),3.99(q,J＝9.6Hz,2H).
compound ig:1H NMR(500MHz,Chloroform-d)δ8.07(d,J＝7.9Hz,1H),7.59–7.53(m,2H),7.44(td,J＝7.4,6.9,2.0Hz,1H),6.88(s,1H),5.91(s,2H),3.92(s,3H),3.89(t,J＝9.8Hz,2H).
biological activity assay
Example 4 insecticidal Activity assay
(1) Method for determining activity of killing plutella xylostella
The method used for testing the biological activity of plutella xylostella is leaf dipping (i.e., proposed by the international Committee for Insecticide Resistance Action Committee, IRAC). The specific operation method comprises the following steps: soaking cabbage leaves in the prepared liquid medicine for 3-5s with straight-head ophthalmologic forceps, taking out tablets, removing redundant liquid medicine, soaking 1 piece of cabbage leaves each time, performing three parallel experiments on each sample, and placing the leaves on the processing paper according to the marking sequence. After the liquid medicine on the leaves is dried, the liquid medicine is respectively put into marked straight test tubes with the length of 10cm, 30 heads of 3-year-old plutella xylostella larvae are respectively inoculated into each test tube, and the test tubes are placed in a standard culture room after the tube openings are covered by gauze. The test uses tolfenpyrad as a positive control medicament and clear water as a negative control medicament. After 48 hours, observing the experimental result, and judging the death standard of the diamondback moth as follows: the body of the insect is shriveled and blackened, and no obvious autonomy exists after the insect is lightly touched by a writing brush; the standard for judging live insects is as follows: the polypide is moist, fresh, cleaned with a brush and kept dynamic. Mortality (%) was calculated from the results of the investigation.
Mortality (%) - (drug-treated mortality-placebo mortality)/(1-placebo mortality) ]. 100
TABLE 2 Plutella xylostella-killing Activity test results for Compounds of the general formula I
Test results show that the compound has good killing activity on diamond back moths except for if, wherein the killing effect of Ib and ie on the diamond back moths is close to that of tolfenpyrad, and the killing rate is about 85 percent at low concentration of 10 mg/L; except for the Rf, the killing activity to the diamondback moth is obviously higher than that to the fluacrypyrim.
Example 5 method for measuring miticidal Activity
The acaricidal activity of the compound is tested by a spraying method, the selected object is Tetranychus cinnabarinus, and the specific operation method comprises the following steps: firstly, diluting a compound into DMF (dimethyl formamide) liquid medicines with different concentrations, carrying out spray treatment on broad bean leaves connected with the same quantity and growth expression, then placing the treated broad bean leaves in a room with the temperature of 24-27 ℃ for observation and culture, recording the growth condition of tetranychus cinnabarinus after 48 hours, and judging the death standard of the tetranychus cinnabarinus as follows: the body of the mite is touched lightly with a brush pen, and if no response is found, the mite is dead. Three control experiments were set up for each concentration in the test and the mortality rate was calculated for each of the three replicates.
Mortality (%) - (drug-treated mortality-placebo mortality)/(1-placebo mortality) ]. 100
TABLE 3 acaricidal Activity test results for Compounds of formula I
Test results show that the compound has a good effect of inhibiting and killing tetranychus cinnabarinus, wherein Ig is close to fluacrypyrim, but other compounds are obviously lower than fluacrypyrim.
Claims (3)
1. The fluorine-containing pyrimidine thioether aromatic ester compound has a structure shown in a general formula I:
2. the use of the compound containing fluoropyrimidine thioether aromatic ester according to claim 1, characterized in that the compound of the general formula I is used as an agricultural or forestry insecticide/acaricide, which has a control effect on agricultural pests and mites.
3. An insecticidal and acaricidal composition comprising a compound of formula i as defined in claim 1 as an active ingredient and an agriculturally or forestry acceptable carrier.
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