CN114605386B - Fluorinated pyrimidine thioether aromatic ester insecticidal acaricide - Google Patents
Fluorinated pyrimidine thioether aromatic ester insecticidal acaricide Download PDFInfo
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- 230000000895 acaricidal effect Effects 0.000 title claims abstract description 18
- 239000000642 acaricide Substances 0.000 title claims abstract description 11
- 230000000749 insecticidal effect Effects 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 description 3
- 150000003568 thioethers Chemical class 0.000 title description 3
- 150000003230 pyrimidines Chemical class 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 241000238876 Acari Species 0.000 claims abstract description 15
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 11
- -1 fluoropyrimidine thioether aromatic ester compound Chemical class 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims 1
- 230000002147 killing effect Effects 0.000 abstract description 14
- 239000002917 insecticide Substances 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000012360 testing method Methods 0.000 description 14
- 241000500437 Plutella xylostella Species 0.000 description 11
- 239000000575 pesticide Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- YYXSCUSVVALMNW-FOWTUZBSSA-N pyriminostrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1COC1=CC(C(F)(F)F)=NC(NC=2C(=CC(Cl)=CC=2)Cl)=N1 YYXSCUSVVALMNW-FOWTUZBSSA-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
- 241000238631 Hexapoda Species 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
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000007788 liquid Substances 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
- 238000003786 synthesis reaction Methods 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
- 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
- 230000009471 action Effects 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229940125890 compound Ia Drugs 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000003208 petroleum 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
- 239000012267 brine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000003921 oil Substances 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
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 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
- WAVYAFBQOXCGSZ-UHFFFAOYSA-N 2-fluoropyrimidine Chemical compound FC1=NC=CC=N1 WAVYAFBQOXCGSZ-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
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 238000003556 assay Methods 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
- 239000012230 colorless oil 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
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011835 investigation Methods 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 230000007935 neutral effect Effects 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
- 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000012865 response to insecticide Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method 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
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- 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)
Abstract
The invention provides a fluoropyrimidine thioether aromatic ester compound, which has a structure shown in a general formula I:wherein R1 is: CH (CH) 3 CH 2 CH 2 CH 2 ‑,CF 3 CH 2 -; r2 is:
Description
The invention belongs to the field of pesticides and acaricides in pesticides, and relates to a fluoropyrimidine thioether aromatic ester pesticide and acaricide and application thereof in preventing and controlling pest mites in agriculture or forestry.
Background art agricultural pests and mites harm the growth of crops, resulting in reduced yield and reduced quality. At present, the control of pest mites mainly depends on chemical pesticides, and because a large number of frequently used pesticides and acaricides are adopted, the pest mites have serious drug resistance to the chemical pesticides, so that the dosage is larger and larger, the control effect is lower and lower, the duration is shortened, the pesticide residue is increased and the like. The development and application of novel insecticidal and acaricidal agents with different action mechanisms are effective means for solving the problem of pest resistance. The fluacrypyrim is a fluorinated pyrimidine acrylic ester acaricide which is researched and developed by Pasteur company and Japanese Caon company, is mainly used for controlling fruit trees, and has excellent biological performance especially for controlling various mites such as apple red spiders, citrus red spiders and the like in fruit trees such as apples, oranges, pears and the like. Although the compounds (I) of the present invention and the pyriminostrobin each contain a trifluoromethyl pyrimidine ring in structure, there is no disclosure in the prior art of the compounds of the formula I according to the present invention and their use as agricultural insecticidal acaricides.
The invention aims to provide an insecticidal and acaricidal agent which has novel structure, simple and convenient synthesis method, safety and high efficiency and can be used for preventing and controlling agricultural or forestry pest mites.
The technical scheme of the invention is as follows:
a fluorine-containing pyrimidine thioether aromatic ester compound has a structure shown in a general formula I:
wherein R1 is: CH (CH) 3 CH 2 CH 2 CH 2 -,CF 3 CH 2 -; r2 is:
。
the compounds of the general formula I according to the invention can be prepared by the following processes:
wherein R1 and R2 are as defined above, and X is Cl or Br.
The compound of the formula II and the compound of the formula III are subjected to esterification reaction (or substitution reaction) in ethyl acetate (or DMF) by using triethylamine (or potassium carbonate) as a catalyst at room temperature or under heating to prepare the compound of the formula I. The specific preparation method is shown in the synthetic example of the invention. Table 1 shows the structure and appearance 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 (formula I) of the invention is used as agricultural insecticide and acaricide, and has the advantages of novel structure, simple and convenient preparation and insect and mite treatment. The compound has good inhibiting and killing effects on plutella xylostella and tetranychus cinnabarinus, and can achieve the excellent effect of simultaneously controlling insect pest mites of agriculture and forestry. Compared with the commercial pesticide tolfenpyrad, the killing effect of Ib and ie on plutella xylostella is close to that of tolfenpyrad. Compared with the commercial acaricide pyriminostrobin, the killing rate of the plutella xylostella is obviously higher than that of the pyriminostrobin, wherein the killing rate of Ig on tetranychus cinnabarinus is close to that of the pyriminostrobin. 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 pesticide-resistant agricultural pest mites commonly existing at present, and has good development and application prospects as a novel variety of pesticides with the functions of killing insects and mites.
The compound can be used independently or in combination with other active substances to improve the comprehensive performance of the product.
The invention also comprises an insecticidal and acaricidal composition taking 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 can be made within the scope of the present invention as defined in the appended claims.
Detailed Description
The following synthetic examples, green test results, are useful for further illustration of the invention and are not meant to limit the invention.
Synthesis example
Example 1 preparation of Compound Ia:
(1) Synthesis of intermediate compounds of formula ii:
in a 250mL three-port reaction flask, 19.62g (0.10 mol) of 2-mercapto-4-hydroxy-6-trifluoromethyl pyrimidine and 16.59g (0.12 mol) of potassium carbonate are added into 50mL of DMF, and after stirring at room temperature for 10min, 15.07g (0.11 mol) of n-bromobutane is added dropwise, after the dropwise addition, the reaction is completed at room temperature for 3h, TLC monitors that the reaction is complete, the reaction solution is poured into 150mL of water, hydrochloric acid is added dropwise to be neutral under stirring, and a solid is separated. Suction filtration, washing, filter cake collection and drying are carried out, thus obtaining the compound 2- (n-butylsulfanyl) -4-hydroxy-6- (trifluoromethyl) pyrimidine with the yield of 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-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) To a 250mL three-necked flask, 13.86g (0.1 moL) of 2-chloronicotinonitrile, 11.21g (0.1 moL) of p-fluorophenol and 16.59g (0.12 moL) of potassium carbonate were added, and then 100mL of DMF was added as a reaction solvent, followed by stirring, reflux reaction for 3 hours, TLC was monitored to complete the reaction, 150mL of water was added, and a white solid was precipitated to give an intermediate 2- (4-fluorophenoxy) nicotinonitrile in a yield of 92%.
2) To a 250mL three-necked flask, 2- (4-fluorophenoxy) nicotinonitrile and potassium hydroxide (0.1 mol) obtained in the above step 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 result of TLC monitoring showed that the reaction was complete. Reducing the reaction temperature, adding hydrochloric acid to adjust to be slightly acidic, precipitating solid, carrying out suction filtration and drying to obtain crude 2- (4-fluorophenoxy) nicotinic acid, wherein the yield is 62%.
3) In a 250mL single-neck round bottom flask, 23.3g (0.1 mol) of 2- (4-fluorophenoxy) nicotinic acid and 17.85g (0.15 mol) 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 4 hours, TLC monitoring reaction is complete, toluene and residual thionyl chloride are removed by reduced pressure distillation, and 2- (4-fluorophenoxy) nicotinyl chloride is obtained as a white solid with the yield of 98%.
(3) Synthesis of Compound Ia:
2.52g (10.0 mmol) of 2- (n-butylsulfanyl) -4-hydroxy-6- (trifluoromethyl) pyrimidine and 1.21g (12.0 mmol) of triethylamine are added into a 100mL three-necked flask, then 20mL of ethyl acetate is added as a reaction solvent, the mixture is stirred for 0.5h at room temperature, 2.64g (10.5 mmol) of 2- (4-fluorophenoxy) nicotinoyl chloride is added in portions, the reaction temperature is controlled at room temperature, the reaction is carried out for 3 to 5h, and TLC monitors the completion of the reaction. After cooling, 60mL of water was added to the reaction solution, extraction was performed with ethyl acetate (3×30 mL), the organic layer was washed with brine (2×20 mL) and dried over anhydrous sodium sulfate, 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 target compound ia. The oil was colorless and the yield was 67%.
Example 2 preparation of Compound ic:
into a 250mL three-necked flask, 25.2g (0.1 mol) of 2- (n-butylsulfanyl) -4-hydroxy-6- (trifluoromethyl) pyrimidine and 12.1g (0.12 mol) of triethylamine were added, then 200mL of ethyl acetate was added as a reaction solvent, the mixture was stirred at room temperature for 0.5h, 20.0g (0.105 mol) of p-toluenesulfonyl chloride was added in portions, the reaction temperature was controlled at room temperature, the reaction was completed for 3 to 5h, and TLC was monitored to complete the reaction. After cooling, 100mL of water was added to the reaction solution, extraction was performed with ethyl acetate (3×30 mL), the remaining organic layer was washed with brine (2×20 mL), 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 target compound ic. Colorless oil, yield 65%.
Example 3 preparation of Compound Ig:
in a 100mL three-necked flask, 2- ((2, 2-trifluoroethyl) thio) -4-hydroxy-6- (trifluoromethyl) pyrimidine 2.78g (10.0 mmol) and potassium carbonate 1.66g (12.0 mmol) were added, 20mL of DMF was added as a reaction solvent, stirred at room temperature for 0.5h, methyl 2-chloromethylbenzoate 1.94g (10.5 mmol) was added in portions, the temperature was raised to 85℃and the reaction was continued for 3-5h, and TLC was monitored to be complete. Cooled to room temperature, 60mL of water was added to the reaction solution, extracted with ethyl acetate (3×30 mL), the organic layer was dried over anhydrous sodium sulfate, the remaining ethyl acetate was distilled off under reduced pressure, and the crude product was purified by column chromatography (V (ethyl acetate): V (petroleum ether) =1:10) to give the objective compound i g. White solid, yield 71%.
Compounds Ib, id, ie, if are synthesized in a similar manner to Ia.
The nuclear magnetic data of the compounds of the general formula I of the invention are as follows:
compound la: 1 H 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).
compound ib: 1 H 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).
compound ic: 1 H 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).
compound id: 1 H 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).
compound ie: 1 H 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).
compound if: 1 H 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: 1 H 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 test
Example 4 insecticidal Activity assay
(1) Method for measuring activity of killing plutella xylostella
The method used for testing the biological activity of plutella xylostella was the leaf dipping method (i.e. as proposed by the international committee on pesticide resistance action Insecticide Resistance Action Committee, IRAC). The specific operation method comprises the following steps: soaking cabbage leaves in the prepared medicinal liquid for 3-5s with straight ophthalmic forceps, taking out the tablet, removing redundant medicinal liquid, soaking 1 cabbage leaf each time, performing three parallel experiments on each sample, and placing the leaves on the treatment paper according to the marking sequence. After the liquid medicine on the leaf is dried, the leaf 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 in each test tube, and the mouth of the tube is covered by gauze and then is placed in a standard culture room. The test uses tolfenpyrad as a positive control medicament and clean water as a negative control medicament. After 48 hours, the experimental result is observed, and the death judgment standard of the plutella xylostella is as follows: the insect body is shrunken and blackened, and no obvious autonomy exists after the light touch test of the writing brush is performed; the standard for judging the living insects is as follows: the insect body is moist, fresh and cleaned by a writing brush and kept dynamic. Mortality (%) was calculated from the investigation result.
Mortality (%) = [ (agent treatment mortality-placebo mortality)/(1-placebo mortality) ]. 100
TABLE 2 results of Plutella xylostella killing Activity test of Compounds of general formula I
The test result shows that the compound of the invention has good killing activity to plutella xylostella except if, wherein the killing effect of ib and ie to plutella xylostella is close to that of tolfenpyrad, and the killing rate reaches about 85% under the low concentration of 10 mg/L; except if, the killing activity to plutella xylostella is obviously higher than that of the pyriminostrobin.
Example 5 method for determining acaricidal Activity
The mite killing activity test is carried out on the compound, the test method is a spray method, the test object is tetranychus cinnabarinus, and the specific operation method is as follows: firstly, diluting a compound into DMF liquid medicines with various concentrations, carrying out spray treatment on the broad bean leaves connected with the same quantity and growth state, 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 of the tetranychus cinnabarinus as follows: the body of the mites is lightly touched by a writing brush, and if the mites do not respond at all, the mites are dead. Three control experiments were set up for each concentration in the test, and mortality was calculated for each three parallel experiments.
Mortality (%) = [ (agent treatment mortality-placebo mortality)/(1-placebo mortality) ]. 100
TABLE 3 acaricidal Activity test results for Compounds of the general formula I
The test result shows that the compound has good inhibiting and killing effect on tetranychus cinnabarinus, wherein Ig is close to the pyriminostrobin, but other compounds are obviously lower than the pyriminostrobin.
Claims (3)
1. A fluorine-containing pyrimidine thioether aromatic ester compound has a structure shown in a general formula I:
wherein R1 is: CH (CH) 3 CH 2 CH 2 CH 2 -,CF 3 CH 2 -; r2 is:
。
2. the application of the fluorine-containing pyrimidine thioether aromatic ester compound according to claim 1, which is characterized in that the compound of the general formula I is used as an agricultural or forestry insecticidal acaricide and has a control effect on agricultural pest mites.
3. An insecticidal and acaricidal composition comprising a compound of the general formula i as defined in claim 1 as active ingredient and an agriculturally or forestry acceptable carrier.
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