CN114805197A - Fluorine-containing pyridine acyl urea insecticide and acaricide - Google Patents
Fluorine-containing pyridine acyl urea insecticide and acaricide Download PDFInfo
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- CN114805197A CN114805197A CN202210399158.5A CN202210399158A CN114805197A CN 114805197 A CN114805197 A CN 114805197A CN 202210399158 A CN202210399158 A CN 202210399158A CN 114805197 A CN114805197 A CN 114805197A
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- Prior art keywords
- compound
- fluorine
- acaricide
- mites
- general formula
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- 230000000895 acaricidal effect Effects 0.000 title claims abstract description 17
- 239000000642 acaricide Substances 0.000 title claims abstract description 11
- 239000002917 insecticide Substances 0.000 title claims abstract description 11
- -1 pyridine acyl urea Chemical class 0.000 title claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 8
- 239000011737 fluorine Substances 0.000 title claims abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 241000238876 Acari Species 0.000 claims abstract description 14
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 9
- 230000000749 insecticidal effect Effects 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims 1
- 230000002147 killing effect Effects 0.000 abstract description 15
- 230000002401 inhibitory effect Effects 0.000 abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 17
- 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
- 238000003756 stirring Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000007788 liquid 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
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 241000500437 Plutella xylostella Species 0.000 description 5
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 241000500441 Plutellidae Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010438 heat treatment 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
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000005507 spraying 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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-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
- 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 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
- 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
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000003556 assay Methods 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
- 238000012544 monitoring process Methods 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
- 239000007921 spray Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 1
- 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
- 241000238631 Hexapoda Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 241000233679 Peronosporaceae Species 0.000 description 1
- 241000500439 Plutella 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007605 air drying Methods 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
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product 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
- 230000009977 dual effect Effects 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
- 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
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002045 lasting effect Effects 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
- 230000003129 miticidal effect 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
- 239000000047 product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 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
Abstract
The invention provides a fluorine-containing pyridine acyl urea compound, which has a structure shown as a general formula I:
wherein Y is O or S; r is:
Description
The invention belongs to the field of insecticides and acaricides in pesticides, and relates to a fluorine-containing pyridine acyl urea 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. Fluopyram is a 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 compounds of the present invention and the above-mentioned fluopyram both structurally contain a trifluoromethylpyridine ring, but the compounds of the general formula I according to 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:
a fluorine-containing pyridine acyl urea compound has a structure shown as a general formula I:
the compounds of the general formula I according to the invention can be prepared by the following method:
The 3-chloro-5-trifluoromethyl-2-pyridineformyl isocyanate or 3-chloro-5-trifluoromethyl-2-pyridineformyl thioisocyanate reacts with an amine compound to produce a compound of the general formula I, and the specific 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. The compound has killing activity on diamondback moths, wherein the killing effect on the diamondback moths is good by I-1, I-2, I-3, I-7 and I-8, and the killing rate reaches over 85 percent at the concentration of 100 mg/L. Has inhibiting and killing effect on Tetranychus cinnabarinus, wherein the inhibiting and killing effect of I-7, I-8 and I-9 is good, and the concentration of the inhibiting and killing agent is more than 80% at 200 mg/L. The compound of the invention 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 the pesticide-resistant agricultural pests and mites which commonly exist at present, and has good development and application prospects as a new variety of pesticide with pesticide and mite killing.
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 i-1:
(1) synthesis of intermediate ethyl 2- (3-chloro-5- (trifluoromethyl) pyridin-2-yl) -2-cyanoacetate:
100mL of acetonitrile and 27.2g (0.24mol) of ethyl cyanoacetate were added to a 250mL three-necked flask, 30.4g (0.22mol) of potassium carbonate was added thereto, 43.2g (0.20mol) of 2, 3-dichloro-5-trifluoromethylpyridine was slowly dropped into the three-necked flask with a constant pressure dropping funnel while stirring at room temperature, the mixture was slowly heated to 80 ℃ and then further heated to reflux for 2 hours, and then the reaction was monitored by TLC (a developing solvent was petroleum ether). And after the reaction is completed, the liquid in the flask is brown and transparent, the temperature is reduced to room temperature, 100mL of deionized water is slowly added, the pH value of the system is adjusted to be 2-3 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 is naturally reduced to the room temperature, the suction filtration is carried out, the washing is carried out for three times by 20mL of deionized water, 53.4g of yellow solid is obtained after the drying, and the yield of the crude product is 91.2%.
(2) Synthesis of intermediate 3-chloro-5- (trifluoromethyl) pyridine-2-carboxylic acid:
a500 mL four-necked flask equipped with a mechanical stirring device was charged with 52.7g (0.18mol) of ethyl 2- (3-chloro-5- (trifluoromethyl) pyridin-2-yl) -2-cyanoacetate and 21.6g (0.54mol) of sodium hydroxide, and then 150mL of deionized water was added as a solvent and stirred. Slowly adding 30% aqueous hydrogen peroxide solution dropwise into the reaction system at room temperature, beginning to dissolve yellow solid in the flask, enabling the liquid in the flask to be yellow and transparent, monitoring by TLC (developing agent V (petroleum ether): V (ethyl acetate): 7:1), cooling to room temperature after the reaction is completed, adjusting the pH of the system to be 2-3 by using diluted phosphoric acid, enabling a large amount of white solid to appear in the flask, continuing stirring for 15min, cooling to room temperature, performing suction filtration, washing with 20mL of deionized water for three times, and drying to obtain 33.2g of white solid, wherein the yield of a crude product is 81.6%.
(3) Synthesis of intermediate 3-chloro-5- (trifluoromethyl) pyridine-2-carbonyl chloride:
adding 33.2g (0.15mol) of intermediate 3-chloro-5- (trifluoromethyl) pyridine-2-formic acid into a 250mL single-neck flask, adding 100mL of toluene and 27.4g (0.0.23mol) of thionyl chloride, finally adding 3 drops of DMF, adding a stirring magneton, placing the mixture into a heating device, adding a drying tube and an alkali absorption device, heating to reflux, detecting that the reaction product 3-chloro-5- (trifluoromethyl) pyridine-2-formic acid is completely reacted by TLC when the liquid in the flask is brown and transparent, cooling to room temperature, removing the toluene and the unreacted thionyl chloride by reduced pressure distillation, adding 30g of acetonitrile into the flask to obtain 60.5g (50.4%) of crude acetonitrile solution, and sealing and storing for later use.
(4) Synthesis of I-1:
adding 1.94g (0.02mol) of dry potassium thiocyanate solid into a 100mL three-neck flask, adding 10mL of acetonitrile serving as a solvent, adding one drop of PEG-200 serving as a catalyst, stirring at room temperature, slowly dropwise adding 5.29g (0.01mol) of the acid chloride acetonitrile solution with the content of 50.4% prepared in the previous step by using a constant-pressure dropping funnel, continuously reacting for 2 hours after dropwise adding is finished, taking out a small amount of reaction liquid, monitoring by TLC, heating to 70 ℃ after the acid chloride reaction is finished, slowly dropwise adding a mixture of 1.53g (0.0095mol) of 2-trifluoromethylaniline and 5mL of acetonitrile into a system, and continuously heating to reflux reaction for 2 hours. The reaction was monitored by TLC (developing agent V (petroleum ether): V (ethyl acetate) ═ 1:1) and cooled to room temperature after completion of the reaction of 2-trifluoromethylaniline. And adding 30mL of deionized water into the flask, continuously stirring for 10min, performing suction filtration, washing twice with 10mL of deionized water, and drying to obtain a crude product. Column chromatography gave 3.19g of white solid in 78.6% yield.
I-2, I-3, I-4 and 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 were added to a 250mL three-necked flask, and the mixture was stirred and mixed uniformly in a low-temperature cooling circulator (-10 ℃). 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 dropwise addition, TLC (developing solvent V (petroleum ether): V (ethyl acetate): 7:1) monitors the degree of the acyl chloride reaction in the reaction system, and after the acyl chloride reaction is completed, 50mL of deionized water is added, and the stirring is continued for 15 min. And (3) carrying out suction filtration, washing the filter cake with 20mL of 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) pyridine-2-acyl isothiocyanate:
a250 mL single-neck flask was charged with 100mL of 1, 2-dichloroethane as a solvent, and 30.2g (0.24mol) of oxalyl chloride were added thereto, followed by stirring to be uniform, and a drying tube and an alkali absorber were added thereto. 26.6g (0.12mol) 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 reaction was warmed to reflux and monitored by TLC (developing solvent V (petroleum ether): V (ethyl acetate): 4: 1). After reflux reaction for 2h, cooling to room temperature after 3-chloro-5- (trifluoromethyl) pyridine-2-formamide completely reacts. The solvent and the oxalyl chloride which is not completely reacted are distilled off under reduced pressure to obtain dark yellow transparent liquid, 30g of acetonitrile is added to prepare 58.5g of isocyanate-acetonitrile solution with the content of 48.7 percent, and the solution is sealed in a sample bottle and is stored for standby.
(3) Synthesis of Compounds I-7:
in a 100mL three-necked flask equipped with a stirring magneton, 20mL of acetonitrile as a solvent was added, and 2.61g (0.0095mol) of 2-methyl-4- (perfluoropropan-2-yl) aniline was added, 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 temperature was raised continuously to reflux after completion of the addition, and the reaction was monitored by TLC (developing agent V (petroleum ether): V (ethyl acetate): 7: 1). After the reflux reaction is carried out for 1h, the temperature is reduced to room temperature after the 2-methyl-4- (perfluoropropane-2-yl) aniline reaction is finished. Adding 50mL of deionized water into the flask, continuously stirring for 10min, carrying out suction filtration, washing with deionized water for three times, and drying to obtain 4.49g of white solid with the yield of 85.4%.
I-6, I-8 and 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:
a 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)。
a 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)。
a 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)。
compounds I to 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)。
compounds I to 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)。
a 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 assay
Example 3 insecticidal Activity assay
(1) Method for determining activity of killing plutella xylostella
The specific implementation method comprises the following steps: the samples to be tested 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 percent of Tween-80. Cutting cabbage leaves into round pieces with uniform size and shape, soaking into the prepared liquid medicine with gradient concentration for 15-20s, taking out, repeating each concentration for three times, air drying, and placing the leaves on wet filter paper 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 be 25 ℃, controlling the relative humidity to be 60 percent and controlling the photoperiod to be L: D: 16:8, and observing and recording the growth state of the plutella xylostella. When the culture time is 72h, the death number of the diamondback moth larvae is counted, and the result is the average value of the three groups of experiments.
TABLE 2 Plutella xylostella-killing Activity test results for Compounds of the general formula I
Test results show that the compound has killing activity on diamondback moths, wherein the killing effect on the diamondback moths is good by I-1, I-2, I-3, I-7 and I-8, and the killing rate reaches over 85 percent at the concentration of 100 mg/L.
Example 4 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:
diluting 500mg/L medicinal liquid with 0.1% Tween-80 to obtain samples with different concentrations, adding into a Potter spray tower under pressure of 1.47 × 10 5 MPa. 30 adult mites are inoculated on circular broad bean leaves with the diameter of 5cm, and three groups are arranged for each concentration. And then placing the leaves connected with the adult mites in a Potter spray tower, spraying 1mL of liquid medicine, placing the leaves after spraying treatment in a constant-temperature incubator at 25 ℃ for culturing for 48 hours, 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 formula I
Test results show that the compound has a killing effect on tetranychus cinnabarinus, wherein the killing effect of I-7, I-8 and I-9 is good, and the killing effect is more than 80% at the concentration of 200 mg/L. But the activity is lower than that of fluacrypyrim.
Claims (3)
1. A fluorine-containing pyridine acyl urea compound has a structure shown as a general formula I:
2. the use of the fluorine-containing pyridine acyl urea compound as claimed in claim 1, characterized in that the compound of the general formula I is used as agricultural or forestry insecticides and acaricides, which has 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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| US4533676A (en) * | 1982-05-11 | 1985-08-06 | Bayer Aktiengesellschaft | 2,5-Dihalogenobenzoyl-(thio)urea insecticides |
| CN101461369A (en) * | 2008-09-11 | 2009-06-24 | 王玉亭 | Synergistic insecticidal composition containing novaluron and chlopyrifos, and use thereof |
| CN105153037A (en) * | 2015-09-06 | 2015-12-16 | 青岛科技大学 | Pyrazole ureide compound |
| CN110526863A (en) * | 2019-08-29 | 2019-12-03 | 贵州大学 | The acylthioureas and acyl group carbamide derivative of a kind of trifluoromethyl pyridine and its application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4533676A (en) * | 1982-05-11 | 1985-08-06 | Bayer Aktiengesellschaft | 2,5-Dihalogenobenzoyl-(thio)urea insecticides |
| CN101461369A (en) * | 2008-09-11 | 2009-06-24 | 王玉亭 | Synergistic insecticidal composition containing novaluron and chlopyrifos, and use thereof |
| CN105153037A (en) * | 2015-09-06 | 2015-12-16 | 青岛科技大学 | Pyrazole ureide compound |
| CN110526863A (en) * | 2019-08-29 | 2019-12-03 | 贵州大学 | The acylthioureas and acyl group carbamide derivative of a kind of trifluoromethyl pyridine and its application |
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