CN114805197B - Fluorinated pyridine acyl urea insecticide and acaricide - Google Patents
Fluorinated pyridine acyl urea insecticide and acaricide Download PDFInfo
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- CN114805197B CN114805197B CN202210399158.5A CN202210399158A CN114805197B CN 114805197 B CN114805197 B CN 114805197B CN 202210399158 A CN202210399158 A CN 202210399158A CN 114805197 B CN114805197 B CN 114805197B
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- 230000000895 acaricidal effect Effects 0.000 title claims abstract description 16
- -1 Fluorinated pyridine acyl urea Chemical class 0.000 title claims abstract description 11
- 239000000642 acaricide Substances 0.000 title claims abstract description 9
- 239000002917 insecticide Substances 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 241000238876 Acari Species 0.000 claims abstract description 13
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 15
- 230000000749 insecticidal effect Effects 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims 1
- 230000002147 killing effect Effects 0.000 abstract description 14
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 241000500437 Plutella xylostella Species 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000575 pesticide Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 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
- 230000001276 controlling effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000001263 acyl chlorides Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- DVUFMZZZAYXFTB-UHFFFAOYSA-N 3-chloro-5-(trifluoromethyl)pyridine-2-carboxamide Chemical compound NC(=O)C1=NC=C(C(F)(F)F)C=C1Cl DVUFMZZZAYXFTB-UHFFFAOYSA-N 0.000 description 3
- HXRMCZBDTDCCOP-UHFFFAOYSA-N 3-chloro-5-(trifluoromethyl)pyridine-2-carboxylic acid Chemical compound OC(=O)C1=NC=C(C(F)(F)F)C=C1Cl HXRMCZBDTDCCOP-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VBLXCTYLWZJBKA-UHFFFAOYSA-N 2-(trifluoromethyl)aniline Chemical compound NC1=CC=CC=C1C(F)(F)F VBLXCTYLWZJBKA-UHFFFAOYSA-N 0.000 description 2
- SNIMEAODTKIPAR-UHFFFAOYSA-N 3-chloro-5-(trifluoromethyl)pyridine-2-carbonyl chloride Chemical compound FC(F)(F)C1=CN=C(C(Cl)=O)C(Cl)=C1 SNIMEAODTKIPAR-UHFFFAOYSA-N 0.000 description 2
- QVAUOEHPYOFAQA-UHFFFAOYSA-N 4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-methylaniline Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1N QVAUOEHPYOFAQA-UHFFFAOYSA-N 0.000 description 2
- 239000005783 Fluopyram Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 102000019259 Succinate Dehydrogenase Human genes 0.000 description 2
- 108010012901 Succinate Dehydrogenase Proteins 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- MTHOZIDITGUPLW-UHFFFAOYSA-N ethyl 2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]-2-cyanoacetate Chemical compound CCOC(=O)C(C#N)C1=NC=C(C(F)(F)F)C=C1Cl MTHOZIDITGUPLW-UHFFFAOYSA-N 0.000 description 2
- KVDJTXBXMWJJEF-UHFFFAOYSA-N fluopyram Chemical compound ClC1=CC(C(F)(F)F)=CN=C1CCNC(=O)C1=CC=CC=C1C(F)(F)F KVDJTXBXMWJJEF-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ABNQGNFVSFKJGI-UHFFFAOYSA-N 2,3-dichloro-5-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CN=C(Cl)C(Cl)=C1 ABNQGNFVSFKJGI-UHFFFAOYSA-N 0.000 description 1
- ATRQECRSCHYSNP-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine Chemical group FC(F)(F)C1=CC=CC=N1 ATRQECRSCHYSNP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 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
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- OFZCDISYZAVSTD-UHFFFAOYSA-N C(C)#N.C(=O)=N Chemical compound C(C)#N.C(=O)=N OFZCDISYZAVSTD-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- 241000233679 Peronosporaceae Species 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 235000002098 Vicia faba var. major Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003899 bactericide agent Substances 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
- 238000004440 column chromatography Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- HWPJEJBDGWNMRM-UHFFFAOYSA-N formyl isocyanate Chemical compound O=CN=C=O HWPJEJBDGWNMRM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 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 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides a fluorine-containing pyridine acyl urea compound, the structure of which is shown as a general formula I:
wherein Y is O or S; r is:
Description
The invention belongs to the field of pesticides and acaricides in pesticides, and relates to a fluoropyridine acyl urea-containing 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. Fluopyraclostrobin (Fluopyram) is a succinate dehydrogenase (Succinate dehydrogenase, SDH) inhibitor, is mainly used as a bactericide for preventing and treating gray mold, powdery mildew and downy mildew of crops in agriculture, and is an excellent nematicide.
The compound of the invention and the fluopyram contain trifluoromethyl pyridine ring structurally, but the compound of the general formula I and the application thereof as agricultural insecticidal acaricide are not disclosed in the prior art.
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 pyridine acyl urea 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 processes:
3-chloro-5-trifluoromethyl-2-pyridine formyl isocyanate or 3-chloro-5-trifluoromethyl-2-pyridine formyl thioisocyanate reacts with amine compounds to generate the compound shown in the general formula I, and 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. The compound has killing activity on plutella xylostella, wherein the killing effect on plutella xylostella by I-1, I-2, I-3, I-7 and I-8 is good, and the killing rate reaches more than 85% at the concentration of 100 mg/L. Has inhibiting and killing effects on tetranychus cinnabarinus, wherein the inhibiting and killing effects of I-7, I-8 and I-9 are good, and the concentration of the tetranychus cinnabarinus reaches more than 80 percent under 200 mg/L. The compound is a fluorine-containing pyridine ureide 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 new 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 I-1:
(1) Synthesis of intermediate ethyl 2- (3-chloro-5- (trifluoromethyl) pyridin-2-yl) -2-cyanoacetate:
into a 250mL three-necked flask, 100mL of acetonitrile and 27.2g (0.24 mol) of ethyl cyanoacetate were added, and then 30.4g (0.22 mol) of potassium carbonate was added, and 43.2g (0.20 mol) of 2, 3-dichloro-5-trifluoromethylpyridine was slowly added dropwise with stirring at room temperature using a constant pressure dropping funnel in the three-necked flask, and the mixture was slowly heated to 80℃and then heated to reflux for 2 hours, followed by TLC (developing solvent petroleum ether) monitoring reaction. After the reaction is completed, the liquid in the flask is brown transparent, the temperature is reduced to room temperature, 100mL of deionized water is slowly added, the pH=2-3 of the system is regulated by concentrated hydrochloric acid, a large amount of yellow solid is precipitated at the moment, the stirring is continued for 20min until the temperature of the system naturally reduces to room temperature, the suction filtration is carried out, the liquid is washed three times by 20mL of deionized water, 53.4g of yellow solid is obtained after drying, and the yield of a crude product is 91.2%.
(2) Synthesis of intermediate 3-chloro-5- (trifluoromethyl) pyridine-2-carboxylic acid:
into a 500mL four-necked flask equipped with a mechanical stirring device were charged 52.7g (0.18 mol) of ethyl 2- (3-chloro-5- (trifluoromethyl) pyridin-2-yl) -2-cyanoacetate and 21.6g (0.54 mol) of sodium hydroxide, followed by addition of 150mL of deionized water as a solvent and stirring. Slowly dropwise adding 30g of 30% hydrogen peroxide aqueous solution into a reaction system at room temperature, starting dissolving yellow solid in a flask, monitoring the liquid in the flask in yellow and transparent, cooling to the room temperature after the reaction is complete by TLC (developing solvent V (petroleum ether): V (ethyl acetate) =7:1), regulating the pH of the system to be between 2 and 3 by dilute phosphoric acid, continuously stirring for 15 minutes, cooling to the room temperature, suction filtering, washing with 20mL of deionized water for three times, and drying to obtain 33.2g of white solid with a crude product yield of 81.6%.
(3) Synthesis of intermediate 3-chloro-5- (trifluoromethyl) pyridine-2-carbonyl chloride:
33.2g (0.15 mol) of intermediate 3-chloro-5- (trifluoromethyl) pyridine-2-formic acid, 100mL of toluene and 27.4g (0.23 mol) of thionyl chloride are added into a 250mL single-neck flask, finally 3 drops of DMF are added, the mixture is filled into a stirring magnet, the mixture is placed into a heating device, a drying tube and an alkali absorption device are added, the mixture is heated to reflux, when the liquid in the flask is in a brown transparent state, the reaction of the reactant 3-chloro-5- (trifluoromethyl) pyridine-2-formic acid is detected by TLC, the mixture is cooled to room temperature, toluene and unreacted thionyl chloride are removed by reduced pressure distillation, 30g of acetonitrile is added into the bottle, 60.5g (50.4%) of crude acetonitrile solution is obtained, and the mixture is stored in a sealed manner for standby.
(4) Synthesis of I-1:
1.94g (0.02 mol) of dry potassium thiocyanate solid is added into a 100mL three-neck flask, 10mL of acetonitrile is added as a solvent, one drop of PEG-200 is added as a catalyst, 5.29g (0.01 mol) of acyl chloride acetonitrile solution with the content of 50.4% prepared in one step is slowly added into a constant pressure dropping funnel for stirring at room temperature, the reaction is continued for 2h after the dropping is finished, a small amount of reaction solution is taken out, TLC monitoring is carried out, after the acyl chloride reaction is completed, the temperature is raised to 70 ℃, and a mixture of 1.53g (0.0095 mol) of 2-trifluoromethylaniline and 5mL of acetonitrile is slowly added into the system in a dropwise manner, and the reaction is continuously heated to reflux reaction for 2h. TLC (developing solvent V (petroleum ether): V (ethyl acetate) =1:1) monitored the reaction, and after the reaction of 2-trifluoromethylaniline was completed, the reaction was cooled to room temperature. 30mL of deionized water is added into the flask, stirring is continued for 10min, suction filtration is carried out, 10mL of deionized water is used for washing twice, and drying is carried out, thus obtaining a crude product. Column chromatography gave 3.19g of a white solid in 78.6% yield.
I-2, I-3, I-4, I-5 were prepared in a similar manner.
Example 2 preparation of Compound I-7:
(1) Synthesis of intermediate 3-chloro-5- (trifluoromethyl) pyridine-2-carboxamide:
100mL of concentrated ammonia water and 50mL of acetonitrile are added into a 250mL three-neck flask, and the mixture is placed in a cryocooling circulator (-10 ℃) and stirred uniformly. A solution of 60.5g (50.4%) of 3-chloro-5- (trifluoromethyl) pyridine-2-carbonyl chloride in acetonitrile was transferred to a constant pressure dropping funnel and slowly added dropwise to the flask. After the completion of the dropping, TLC (developing agent is V (petroleum ether): V (ethyl acetate) =7:1) monitors the reaction degree of the acyl chloride in the reaction system, and 50mL of deionized water is added after the acyl chloride is completely reacted, and stirring is continued for 15min. Suction filtration, washing the filter cake with 20mL deionized water for three times, and drying to obtain 26.6g of white powdery solid with the yield of 89.1%.
(2) Synthesis of intermediate 3-chloro-5- (trifluoromethyl) pyridin-2-yl isothiocyanate:
100mL of 1, 2-dichloroethane as a solvent and 30.2g (0.24 mol) of oxalyl chloride were added to a 250mL single-necked flask, and the mixture was stirred well, followed by addition of a drying tube and an alkali absorbing device. 26.6g (0.12 mol) of 3-chloro-5- (trifluoromethyl) pyridine-2-carboxamide synthesized in the above step was weighed and added to the flask in portions with stirring. After addition, the temperature was raised to reflux and the reaction monitored by TLC (developing solvent V (petroleum ether): V (ethyl acetate) =4:1). After 2h of reflux reaction, the reaction mixture is cooled to room temperature after the 3-chloro-5- (trifluoromethyl) pyridine-2-carboxamide is completely reacted. The solvent and the unreacted complete oxalyl chloride are distilled off under reduced pressure to obtain a dark yellow transparent liquid, 30g of acetonitrile is added to prepare 58.5g of isocyanate-acetonitrile solution with 48.7 percent of content, and the mixture is sealed in a sample bottle for cooling.
(3) Synthesis of Compound I-7:
into a 100mL three-necked flask equipped with a stirring magnet, 20mL of acetonitrile was added as a solvent, followed by 2.61g (0.0095 mol) of 2-methyl-4- (perfluoropropan-2-yl) aniline, and the mixture was stirred well and heated to 60 ℃. 5.15g of the 3-chloro-5- (trifluoromethyl) pyridine-2-acylisothiocyanate-acetonitrile solution prepared in the above step was slowly added dropwise to the reaction system, the dropwise addition was continued until the reflux was reached, and TLC (developing solvent V (petroleum ether): V (ethyl acetate) =7:1) was used for monitoring the reaction. After reflux reaction for 1h, cooling to room temperature after the reaction of 2-methyl-4- (perfluoropropane-2-yl) aniline is finished. 50mL of deionized water is added into the flask, stirring is continued for 10min, suction filtration is carried out, the deionized water is washed for three times, and drying is carried out, so that 4.49g of white solid is obtained, and the yield is 85.4%.
I-6, I-8, I-9 were prepared in a similar manner.
The nuclear magnetic data of the compounds of the general formula I of the invention are as follows:
compound i-1: 1 H NMR(500MHz,Chloroform-d)δ：12.10(s,1H),10.94(s,1H),8.86(d,J＝1.8Hz,1H),8.20(d,J＝1.9Hz,1H),7.96(d,J＝8.1Hz,1H),7.76(d,J＝7.9Hz,1H),7.66(t,J＝7.8Hz,1H),7.47(t,J＝7.7Hz,1H)。
compound i-2: 1 H NMR(500MHz,Chloroform-d)δ：12.02(s,1H),11.82(s,1H),9.09(s,1H),8.74(d,J＝1.9Hz,1H),7.88(d,J＝8.5Hz,1H),7.64(s,1H),7.57(d,J＝8.6Hz,1H),2.38(s,3H)。
compound i-3: 1 H NMR(500MHz,Chloroform-d)δ：11.65(s,1H),11.02(s,1H),8.87(d,J＝1.9Hz,1H),8.22(d,J＝1.9Hz,1H),7.79(d,J＝2.2Hz,1H),7.50(s,1H),2.49(s,3H)。
compound i-4: 1 H NMR(500MHz,Chloroform-d)δ：11.71(s,1H),10.73(d,J＝6.0Hz,1H),9.05(s,1H),8.69(d,J＝2.0Hz,1H),7.43–7.38(m,2H),7.19(d,J＝8.1Hz,2H),6.99–6.94(m,2H),6.94–6.89(m,2H),4.84(d,J＝5.7Hz,2H),2.28(s,3H)。
compound i-5: 1 H NMR(500MHz,Chloroform-d)δ：11.71(s,1H),10.71(t,J＝5.7Hz,1H),9.05(s,1H),8.69(d,J＝1.9Hz,1H),7.42–7.36(m,2H),7.32(d,J＝8.0Hz,2H),4.83(d,J＝5.8Hz,2H),1.27(d,J＝1.2Hz,9H)。
compound i-6: 1 H NMR(500MHz,Chloroform-d)δ：10.57(s,1H),9.09(s,1H),8.66(d,J＝2.0Hz,1H),7.81(d,J＝8.8Hz,2H),7.77(t,J＝7.5Hz,1H),7.52(t,J＝7.5Hz,1H)。
compound i-7: 1 H NMR(500MHz,Chloroform-d)δ：10.48(s,1H),9.08(s,1H),8.71(d,J＝2.2Hz,1H),7.92(d,J＝8.5Hz,1H),7.59(s,1H),7.57(d,J＝9.1Hz,1H),2.39(s,3H)。
compound i-8: 1 H NMR(500MHz,Chloroform-d)δ：10.80(s,1H),9.11(d,J＝2.1Hz,1H),8.71(d,J＝2.2Hz,1H),7.81(d,J＝2.4Hz,1H),7.70(d,J＝2.7Hz,1H),2.45(s,3H)。
compound i-9: 1 H NMR(500MHz,Chloroform-d)δ：8.98(s,1H),8.61(d,J＝2.0Hz,1H),7.37(d,J＝8.4Hz,2H),7.30–7.26(m,2H),4.46(d,J＝6.0Hz,2H),1.27(s,9H)。
biological Activity test
Example 3 insecticidal Activity assay
(1) Method for measuring activity of killing plutella xylostella
The specific implementation method is as follows: the test samples are mixed liquid medicine with the concentration of 500mg/L prepared by the compound and DMF, and then the mixed liquid medicine is diluted into liquid medicine with different concentration gradients by using 0.1% Tween-80. Cutting cabbage leaves into discs with uniform size and shape, soaking the discs into the prepared medicinal liquid with gradient concentration for 15-20s, taking out, repeating each concentration for three times, airing, and placing the leaves on filter paper wetted in a culture dish. And (3) placing 30 plutella xylostella larvae with the same growth state in a culture dish, controlling the temperature in the culture dish to 25 ℃, controlling the relative humidity to 60%, controlling the photoperiod to LD=16:8, and observing and recording the growth state of plutella xylostella. And when the culture time is 72 hours, counting the death number of the plutella xylostella larvae, wherein the result is the average value of three groups of experiments.
TABLE 2 results of Plutella xylostella killing Activity test of Compounds of general formula I
The test results show that the compound has killing activity on plutella xylostella, wherein the killing effect on plutella xylostella by I-1, I-2, I-3, I-7 and I-8 is good, and the killing rate reaches more than 85% at the concentration of 100 mg/L.
Example 4 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:
diluting the prepared 500mg/L medicinal liquid with 0.1% Tween-80 to obtain samples with different concentrations, adding into a Potter spray tower, and setting pressure to 1.47×10 5 And (5) MPa. 30 mites are inoculated on round broad bean leaves with the diameter of 5cm, and three groups are arranged for each concentration. Then placing the leaf blade with the mite in a Potter spray tower, spraying 1mL of liquid medicine, placing in a constant temperature incubator at 25 ℃ for culturing for 48 hours after spray treatment, observing and recording the death number of the tetranychus cinnabarinus, and calculating the death rate of the mites according to a formula.
TABLE 3 acaricidal Activity test results for Compounds of the general formula I
The test result shows that the compound has a good inhibition effect on tetranychus cinnabarinus, wherein the inhibition effect of I-7, I-8 and I-9 is good, and the concentration of the compound reaches more than 80% at 200 mg/L. But the activity is lower than that of the pyriminostrobin.
Claims (3)
1. A fluorine-containing pyridine acyl urea compound has a structure shown in a general formula I:
2. the use of a fluoropyridine acyl urea compound according to claim 1, which is characterized in that the compound of the general formula I is used as agricultural or forestry insecticidal acaricide and has 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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