Molecules having pesticidal utility, compositions and pest control methods related thereto
阅读说明：本技术 具有杀有害生物效用的分子、组合物以及与其相关的有害生物控制方法 (Molecules having pesticidal utility, compositions and pest control methods related thereto ) 是由 T·P·马丁 小罗纳德·罗斯 R·J·海姆斯特拉 J·D·埃克尔巴格 T·K·特鲁林格 R 于 2019-03-21 设计创作，主要内容包括：本公开涉及对节肢动物门、软体动物门和线虫动物门中的有害生物具有杀有害生物效用的分子的领域,生产此类分子的方法,在此类方法中使用的中间体,含有此类分子的杀有害生物组合物,以及使用此类杀有害生物组合物对抗此类有害生物的方法。这些杀有害生物组合物可以例如用作杀蜱螨亚纲动物剂、杀昆虫剂、杀螨剂、杀软体动物剂、和杀线虫剂。此文件公开了具有下式(“式一”)的分子。<Image he="292" wi="700" file="DDA0002615294180000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present disclosure relates to the field of molecules having pesticidal utility against pests in the phyla arthropoda, mollusca and nematoda, methods of producing such molecules, intermediates used in such methods, pesticidal compositions containing such molecules, and methods of using such pesticidal compositions to combat such pests. These pesticidal compositions may be used, for example, as acaricidal agents, insecticides, acaricides, molluscicides, and nematicides. This document disclosesMolecules having the formula ("formula one") are provided.)
1. A molecule according to formula one
Wherein:
(A)R1selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(B)R2selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(C)R3selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(D)R4selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(E)R5selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(F)R6is H;
(G)R7selected from the group consisting of: F. cl, and Br;
(H)R8selected from the group consisting of: F. cl, and Br;
(I)R9is H;
(J)Q1selected from the group consisting of O and S;
(K)Q2selected from the group consisting of O and S;
(L)R10selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)1-C3) Alkyl OC (═ O) (C)1-C3) An alkyl group;
(M)R11selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(N)R12selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(O)R13selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(P)R14selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(Q)R15selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Haloalkyl, (C)1-C3) Alkylphenyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl, (C)1-C3) Alkyl OC (═ O) (C)1-C3) Alkyl, and C (═ O) (C)1-C3) An alkyl group;
(R)R16、R17、R18、R19and R20Independently selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、NH2、OH、SF5、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, (C)2-C3) Alkenyl, (C)2-C3) Haloalkenyl, and N (R)21)C(＝O)(R22) Wherein R is16、R17、R18、R19And R20At least one of andnot more than two are N (R)21)C(＝O)(R22)；
(S)R21Selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Haloalkyl, (C)2-C3) Haloalkenyl, (C)1-C3) Alkylphenyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl, (C)1-C3) Alkyl OC (═ O) (C)1-C3) Alkyl, C (═ O) (C)1-C3) Alkyl, and phenyl;
(T)R22selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-aryl, (C)1-C6) alkyl-S (═ O)n-heterocyclyl (C)2-C6) alkenyl-S (═ O)n-(C1-C6) Alkyl, (C)2-C6) alkenyl-S (═ O)n-(C2-C6) Alkenyl, (C)2-C6) alkenyl-S (═ O)n-aryl, (C)2-C6) alkenyl-S (═ O)n-a heterocyclic group,
wherein n is 0, 1, or 2, and
wherein each of said alkyl and alkenyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) Cycloalkyl radicals, and
wherein each of said aryl and heterocyclyl groups may be substituted with one or more substituents selected from the group consisting of: (C)1-C3) Alkyl, F,Cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) A cycloalkyl group; and
n-oxides, agriculturally acceptable acid addition salts, salt derivatives, solvates, ester derivatives, crystalline polymorphs, isotopes, resolved stereoisomers, tautomers, pro-insecticides of a molecule of formula one,
provided that the following molecules are excluded
2. The molecule of claim 1, wherein the molecule has a structure according to formula two
3. A molecule according to any of the preceding claims, wherein R1Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
4. A molecule according to any of the preceding claims, wherein R2Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
5. A molecule according to any of the preceding claims, wherein R3Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
6. The molecule of any one of the preceding claimsWherein R is4Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
7. A molecule according to any of the preceding claims, wherein R5Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
8. A molecule according to any of the preceding claims, wherein R2、R3And R4Is at least one of SF5。
9. A molecule according to any of the preceding claims, wherein R7Is Cl.
10. A molecule according to any of the preceding claims, wherein R8Is Cl.
11. A molecule according to any of the preceding claims, wherein R7And R8Are not the same substituent.
12. The molecule of any preceding claim, wherein Q1Is O.
13. The molecule of any preceding claim, wherein Q2Is O.
14. A molecule according to any of the preceding claims, wherein R10Is H.
15. A molecule according to any of the preceding claims, wherein R11Is H.
16. A molecule according to any of the preceding claims, wherein R12Selected from the group consisting of: H. f, Cl, CH3And CF3。
17. A molecule according to any of the preceding claims, wherein R13Selected from the group consisting of: F. cl, CH3And OCH3。
18. A molecule according to any of the preceding claims, wherein R14Selected from the group consisting of: H. f, and Cl.
19. A molecule according to any of the preceding claims, wherein R15Is H.
20. The molecule of any one of the preceding claims, wherein:
(a)R16、R18、R19and R20Independently selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、NH2、OH、SF5、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, (C)2-C3) Alkenyl group, and (C)2-C3) Haloalkenyl, and R17Is N (R)21)C(＝O)(R22) (ii) a Or
(b)R16、R17、R19And R20Independently selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、NH2、OH、SF5、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, (C)2-C3) Alkenyl group, and (C)2-C3) Haloalkenyl, and R18Is N (R)21)C(＝O)(R22)。
21. A molecule according to any of the preceding claims, wherein R21Is H.
22. A molecule according to any of the preceding claims, wherein R22Is selected fromA group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-aryl, (C)1-C6) alkyl-S (═ O)n-heterocyclyl, wherein n ═ 0, 1, or 2, and wherein each of said alkyl and alkenyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) Cycloalkyl, and wherein each of said aryl and heterocyclyl groups may be substituted with one or more substituents selected from the group consisting of: (C)1-C3) Alkyl, F, Cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) A cycloalkyl group.
23. A molecule according to any of the preceding claims, wherein R22Selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-phenyl, (C)1-C6) alkyl-S (═ O)n-pyridinyl, wherein n ═ 0, 1, or 2, and wherein each of said alkyl and alkenyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, and I, and wherein each of said phenyl and pyridyl groups may be selected from one or more of the group consisting ofSubstituted by one substituent: F. cl, Br, and I.
24. The molecule of any one of the preceding claims, wherein:
R1is H;
R2selected from the group consisting of: H. f, Cl, and CF3；
R3Selected from the group consisting of: H. f, and Cl;
R4selected from the group consisting of: H. f, Cl, and CF3；
R5Is H;
R7is Cl;
R8is Cl;
Q1is O;
Q2is O;
R10is H;
R11is H;
R12is H;
R13is Cl;
R14is H;
R15is H;
R16is F;
R17is N (R)21)C(＝O)(R22)；
R18Is F;
R19is H;
R20is H;
R21is H; and is
R22Selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-phenyl, (C)1-C6) alkyl-S (═ O)n-a pyridyl group,
wherein n is 0, 1, or 2;
wherein each of the alkyl, alkenyl, phenyl, and pyridyl groups may be substituted with one or more substituents selected from the group consisting of F and Cl.
25. The molecule of any one of the preceding claims, wherein:
R1is H;
R2selected from the group consisting of: H. f, Cl, and CF3；
R3Selected from the group consisting of: H. f, and Cl;
R4selected from the group consisting of: H. f, Cl, and CF3；
R5Is H;
R7is Cl;
R8is Cl;
Q1is O;
Q2is O;
R10is H;
R11is H;
R12is H;
R13is Cl;
R14is H;
R15is H;
R16is F;
R17is H;
R18is N (R)21)C(＝O)(R22)；
R19Is H;
R20is H;
R21is H; and is
R22Selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-phenyl, (C)1-C6) alkyl-S (═ O)n-a pyridyl group,
wherein n is 0, 1, or 2;
wherein each of the alkyl, alkenyl, phenyl, and pyridyl groups may be substituted with one or more substituents selected from the group consisting of F and Cl.
26. The molecule of claim 1, wherein the molecule is selected from table 2 and the group consisting of: f2, F3, F4, F5, F6, F7, F8, F9, F10, F11, F12, F13, F14, F15, F16, F17, F18, F19, F22, F23, F24, F25, F26, F27, F28, F29, F30, F31, F32, F33, F34, F35, F37, F39, F42, F44, F45, F46, F47, F48, F49, F50, F51, and F52.
27. The molecule of claim 1, wherein the molecule is selected from table 2 and the group consisting of: f3, F5, F6, F10, F12, F13, F14, F15, F16, F17, F18, F19, F23, F27, F28, F29, F31, F32, F37, F39, F46, F47, and F49.
28. The molecule of claim 1, wherein the molecule is selected from table 2 and the group consisting of: f15, F16, F17, F18, F19, F21, F23, F24, F25, F32, F34, and F46.
29. A composition comprising the molecule of any one of the preceding claims, further comprising a carrier.
30. The composition of claim 29, further comprising an active ingredient.
31. A method of controlling pests, the method comprising applying to a locus a pesticidally effective amount of the composition of any one of claims 29-30.
Technical Field
The present disclosure relates to the field of molecules having pesticidal utility against pests in the phyla arthropoda, mollusca and nematoda, methods of producing such molecules, intermediates used in such methods, pesticidal compositions containing such molecules, and methods of using such pesticidal compositions to combat such pests. These pesticidal compositions may be used, for example, as acaricidal agents, insecticides, acaricides, molluscicides, and nematicides.
Background
"many of the most dangerous human diseases are transmitted by insect vectors" (river et al). "historically, malaria, dengue fever, yellow fever, plague, filariasis, louse borne typhus, trypanosomiasis (trypanomyias), leishmaniasis, and other mediator-transmitted diseases caused human disease and death more than the sum of all other causes in the early 17 th to 20 th century" (Gubler). Mediator-transmitted diseases account for about 17% of global parasitic and infectious diseases. Malaria alone causes over 800,000 deaths each year, with 85% occurring in children under the age of five. There are about 5 million to about 1 million cases of dengue fever per year. 250,000 to 500,000 cases of dengue hemorrhagic fever (Matthews) also occur annually. Mediator control plays a crucial role in the prevention and control of infectious diseases. However, resistance to insecticides, including resistance to multiple insecticides, occurs in all insect species that are the major vectors of human disease (river et al). More recently, more than 550 arthropod species have developed resistance to at least one pesticide (Whalon et al). Furthermore, cases of insect resistance continue to exceed the number of herbicide and fungicide resistance cases to date (Sparks et al).
Each year, insects, plant pathogens, and weeds destroy more than 40% of all food production. This loss occurs despite the application of pesticides and the use of a wide variety of non-chemical control measures (such as crop rotation) and biological control measures. If only a portion of this food could be saved, it could be used to live more than three billion people in the world who are malnourished (dietary).
Plant parasitic nematodes are one of the most common pests, and are usually one of the most concealed and expensive pests. It is estimated that losses attributable to nematodes range from about 9% in developed countries to about 15% in underdeveloped countries. However, investigations of 35 states in the united states on various crops have indicated that losses caused by nematodes are as high as 25% (Nicol et al).
Notably, gastropods (slugs and snails) are pests of less economic importance than other arthropods or nematodes, but in some places they can reduce yields by a large amount, severely affect the quality of the harvested product, and transmit human, animal, and plant diseases. Although only a few dozen gastropod species are serious regional pests, a few species are important pests on a global scale. In particular, gastropods can affect a wide variety of agricultural and horticultural crops, such as arable land, pasture (pastoral), and fiber crops; vegetables; shrubs and tree fruits; medicinal herbs; and ornamental plants (Speiser).
Termites cause damage to all types of private and public structures, as well as agricultural and forestry resources. It is estimated that in 2005, termites annually inflict damage in excess of $ 500 billion per year (Korb).
Thus, for many reasons, including those described above, the need to develop new pesticides continues, which is expensive (estimated at about $ 2.56 billion per pesticide in 2010), time consuming (on average about 10 years per pesticide), and difficult (the american plant protection association (CropLife America)).
Certain references cited in this disclosure
CropLife America [ American plant protection Association ], The Cost of New agricultural product discovery, Development & Registration, and Research & Development predictions for The Future [ Cost of New Agrochemical discovery, Development and Registration and Future Research and Development predictions ], 2010.
Drewes, m., Tietjen, k., Sparks, t.c., High-Throughput Screening in agricultural chemical Research, modem Methods in Crop Protection Research, Part I, Methods for the Design and Optimization of New Active Ingredients [ High Throughput Screening in agrochemical Research, Modern Methods in Crop Protection Research, Part I, Methods for designing and optimizing New Active Ingredients ], edited by Jeschke, p., Kramer, w., Schirmer, u., and mathhias w., pages 1-20, 2012.
Gubler, D., respiratory vectors as a Global Health protocol, emergent Infectious Diseases [ Diseases transmitted as a recurrent mediator of Global Health problems, Emerging Infectious Diseases ], Vol.4, No. 3, p.442-.
Korb, j., terminites, Current Biology [ Termites, modern Biology ], volume 17, No. 23, 2007.
Matthews, G., Integrated Vector Management: Controlling Vectors of Malaria and Other insert Vector boundary Diseases [ Integrated Medium Management: control of malaria vectors and other insect vector transmitted diseases ], chapter 1, page 1, 2011.
Nicol, j., Turner s., Coyne, l., den Nijs, l., Hocksland, l., Tahna-Maafi, z., Current Nematode threads to World Agriculture, Genomic and Molecular genetic Plant-Nematode Interactions [ Current Nematode Threats to World Agriculture, genome and Molecular genetics-Nematode Interactions of plants ], pages 21-43, 2011.
Pimental, D., Pest Control in World Agriculture, Agricultural science, Vol.II, 2009.
River, A., Vezilier, J., Weill, M., Read, A., Gandon, S., Instrument Control of vector-body Diseases, When is Instrument Resistance a Problem? Public Library of science Patholoens [ insect control of mediator-transmitted diseases: when insect resistance becomes an issue? Scientific pathogen public library ], volume 6, stage 8, pages 1-9, 2010.
Spark T.C., Nauen R., IRAC model of action classification and reaction sensitivity management, Pesticide Biochemistry and Physiology (2014) available online 4 Decumber 2014[ IRAC: mode of action classification and management of insecticide resistance, pesticide biochemistry and physiology (2014), accessible online, 12/4/2014 ].
Speiser, B., Molluscides, Encyclopedia of Pest Management [ Molluscicides, Encyclopedia of Pest Management ], Chapter 219, page 506-508, 2002.
Whalon, M., Mota-Sanchez, D., Hollingworth, R., Analysis of Global Pesticide Resistance in Arthropods, Global Pesticide Resistance in Arthropods [ Analysis of Pesticide Resistance of Global Arthropods, Global Pesticide Resistance of Arthropods ], Chapter 1, pages 5-33, 2008.
Definitions used in this disclosure
The examples given in these definitions are generally not exhaustive and should not be construed as limiting the disclosure. It will be appreciated that substituents should comply with chemical bonding rules and steric compatibility constraints with respect to the particular molecule to which they are attached. These definitions are for the purposes of this disclosure only.
The phrase "active ingredient" means a material having activity useful for controlling pests and/or a material useful for helping other materials have better activity for controlling pests, and examples of such materials include, but are not limited to, acaricidal agents, algicides, antifeedants, avicides, bactericides, bird repellents, chemosterilants, fungicides, herbicide safeners, herbicides, insect attractants, insect repellents, insecticides, mammal repellents, mating disruptors, molluscicides, nematicides, plant activators, plant growth regulators, rodenticides, synergists, and virucides (see alanwood. Examples of such materials include, but are not limited to, the materials listed in active ingredient group α.
The phrase "active ingredient group α" (hereinafter, "AIGA") collectively means the following materials:
(1) (3-ethoxypropyl) mercuric bromide, 1, 2-dibromoethane, 1, 2-dichloroethane, 1, 2-dichloropropane, 1, 3-dichloropropene, 1-MCP, 1-methylcyclopropene, 1-naphthol, 2- (octylthio) ethanol, 2,3,3-TPA, 2,3, 5-triiodobenzoic acid, 2,3,6-TBA, 2,4,5-T, 2,4,5-TB, 2,4,5-TP, 2,4-D, 2,4-DB, 2,4-DEB, 2,4-DEP, 2,4-DES, 2,4-DP, 2,4-MCPA, 2,4-MCPB, 2iP, 2-methoxyethylmercuric chloride, 2-phenylphenol, 3,4-DA, 3,4-DB, 3,4-DP, 3, 6-dichloropicolinic acid, 4-aminopyridine, 4-CPA, 4-CPB, 4-CPP, 4-hydroxyphenylethanol, 8-hydroxyquinoline sulfate, 8-phenylmercaptooxyquinoline, abamectin aminomethyl, abscisic acid, ACC, acephate, chlorfenapyr, acetamiprid, housefly phosphorus, acetochlor, triclosan, ethoprophos, acetofenapyr, araxybenzene, acifluorfen, aclonifen, ACN, alap, flupropathrin, acrolein, acrylonitrile, acenaph (acynapapryr), altaic, alfafenafin, alfafa, alachlor, triclosan, boll, albendazole, aldicarb, aldimorph, aldicarb, aldrin, allerin, allelocrin, allicin, chlorpyricin, aloside, aloamine, chlorpyrifos, aldicarb, diclofop-methyl, allyl alcohol, fenobucarb, pentachlorophenonic acid, alpha-cypermethrin, alpha-endosulfan, alpha-cypermethrin, altretamine, aluminum phosphide (aluminum phosphide), ametryn, tebufenpyrad, flumetsulam, amidosulfuron, methiocarb, pyrimethanil, clomazone, aminopyralid, aminotriazole, amicarbazone, amicarbazinate, fumed silica, amorphous silica, alanoperative, fenamidinium, neonicotinoid, pyrimidinol, fenaminostrobilurin, anilofos, metoxuron, anthraquinone, antol, triazoxide, triazamate, propoxur, triazamate, aspirin, Benazolin, ethofenphos, atran, atrazine, aureozyme, abamectin B1, AVG, ivermectin, azaconazole, azadirachtin, oxaziridine, azamethiphos, bentazone, azimsulfuron, azinphosethyl, azinphos-ethyl, azinphos-methyl, azinphos-tryn, azinpropryn, oxifomazine, azoxybenzene, azocyclotin, azophos-ethyl, azoxystrobin, chrysanthemate, oalban, avelins (bann), avelins (bannate), barium hexafluorosilicate, barium polysulphide, barium fluorosilicate, fumonis, copper hydroxycarbonate, copper oxychloride, copper tribasic, BCPC, fluorobutyryl-M, benoxanil, fenbutazone, fenpropazocarb, fenbendazole, benazolin, fenpropyzacarb, benazolin, fencarb, benazolin, fenpyrane, fenbencarb-B, bencarb-ethyl, bencarb-ethyl, ben, Flufenamid, benfuracarb, benfurazane, saflufenacil, benfurazolin, benomyl, clomazone, benoxafos, dimetrazone, bensulfuron methyl, bensultap, bensulfuron methyl, bentazone, benthiavalicarb, diclofen, fenfluramine, benzalkonium chloride, benzalkonium acid, isoxaflutole, cinnoline, benzene hexachloride, bensulfuron methyl, benzimidine, benzobicyclon, endosulfan, benzoxathion, benzofenazam, benzoxaflusulfamide, primisulfamic acid, benzamate, Benzophosphate (benzosphatate), benzothiadiazole, benpropenazole, fenpyroximate (benzoximate), neoyan, benzopyrimidine (benzopymoxan), thifensulfuron methyl, benzoxaflutolone (benzozuocoong), benzoxathion (benzoxate), benzoxate, benzyladenine, beta-cyhalothrin, BHC, thiocyanofen, deltamethrin, dicumone, dicumyl, benoxanil, bensultamide, benoxanil, bensulcotin, benoxanil, benoxa, Bifenazate, bifenox, bifenthrin, diflufenican, bilarbazine, dicofol, bronopol, bioallethrin, pentoxyfen, biothrin, bioresmethrin, biphenyl, pyrithion, thifluzazole, copper thicumazol, methylenebis (x-naphthalene-y-sulfonate) diphenylmercuric (bisphenylmercuric methyl ethylene (x-napthalene-y-sulfonate)), bispyribac, bistrifluron, dimehypo, fenthiobischlorophenol, bitazone, diclazarone, diclofen S, borax, bordeaux mixture, boric acid, leucogli, BPPS, brassinolide, ethylbrassinolide, pissodan, brodifen, brofenflurazone, brofenflurazon ether (brofenproprenx), brofenvalerate, flufenamide, brofenfluridone, dibromofluridone, brofenflururon, phosphofos, bromfenapyr (lophos), bromfenamate, bromphen, Fulvox-nitrile, bromobutyrolac, bromosilrin, bromfenamid, bromo-DDT, chlorfenapyr, bromophos (bromofos), bromomethane, bromophos (bromophos), ethyl bromophos, bromopropylate, bromothalonil, bromoxynil, bromoatrazine, bromuconazole, bronopol, BRP, BTH, dimethrin, dimethoate, tebuconazole, brefel, buprofezin, berberidis mixture, busulfan, carbofuran, butachlor, butafenacil, butenafluorofen, benethrin, teflufen, butfenphos, butfenpropathrin, butfenthiuron, buthiocarb, butfenpropathrin, butfenthiuron, butfenpropathrin, butrox, butirobutrox, butrox, butrafenone, butynol, butynoneuron, buthiopyr, buthiol, buthiopyr, buthiophos, buthion, buthiorochlor, buthion, Calcium chloride, calcium arsenate, calcium chlorate, calcium cyanamide, calcium cyanide, calcium polysulphide, calcium diuron, fenacet, fenamiphos, camphor, captafol, captan, metam, molocarb, cloxacarb, carbaryl (carbaryl), carbaryl, casfop, carbendazim, carfentrazone, carbofop, carbofuran, carbon tetrachloride, carbonyl sulfide, thiophosphoryl, malathion (carbophos), carbosulfan, carbofuran, cydiocarb, carboxin, carfentrazone, propidin, captan, carvacrol, CAVP, CDAA, CDEA, CDEC, petyne, CEPC, sella, hydrazone, sabam, cheroket, chenet mixed liquor, quinalphos, methyl quinalphos-methyl, fenthion-methyl, fenpropathex, fenpropathyl, fenpropathrin (fenpropathrin), fenpyrone, fenpropidium, fenpyrone, fenpropine, fenpropidium, fenpropinqite, chlorase, oxamyl, chloramine phosphate, chloramphenicol, diammine, benzoquinone tetrachloride, butachlor, chlorantraniliprole, clodinafop-propargyl, clonidine, chlorfenapyr, chlorbenzuron, borneolum, chlorsulfuron, clodinafop-propargyl, chlordane, chlordecone, chlordimeform, prallethrin, rimonazide, ethephon, chlorfenamidine, chlorfenapyr hydrochloride, varroak, chlorfenapyr, benzimidazole, chlorfenapyr, chlorsulfuron, oat ester, clofenpyr, dichlorvos, chlorfenvinphos, chlorfenapyr, chlorsulfuron, chloride, chloro-IPC, chlormephos, chlormequat, sulone, metofen, chlorpropham, mechlorvinphos, cumyl, ethazine, chlorfenapyr, chlorodinafop, chlorfenapyr, chlorofenapyr, chlorfenapyr, propargyl, chlorothalonil, clomazone, chlorsulfuron (chloroxifenidim), chlorsulfuron (chloroxuron), chlorfenapyr (chloroxuron), oxypyr, triclopyr, chlorfenthion, chloropyrazole, methicillin, chlorpyrifos-methyl, tetrachloroquinoxaline, chlorsulfuron, dichlorvos, chloramben, chlorfenapyr, chlortoluron, clofenapyr, chitosan, cholecalciferol, choline chloride, chromafenozide, cyclohexylmitate, trinexapac-ethyl (cimeacarb), trinexapac-ethyl (cimetacarb), cyfluthrin I, cyfluthrin II, guar, indomethadyl, cinmethylin, cinosulfuron, fenchloramide, pyroxsulam, cis-resmethrin, clofenpropathrin, clethon, clethodim, clenbuterol, chlorpyrifos, chlorpheniramine, clofenthiuron, clofenpropiconazole, clofenpropidium, chlorpyrifos-methyl, chlorpyrifos, clofenthiuron, chlorpyrifos-methyl, clofenthiuron, chlorpyrifos-methyl, chloropropionic acid, clomazone, clomeprop, cloacal, clomazone, beclomethazine, cloquintocet-mexyl, cloransulam, closantel, clothianidin, clotrimazole, clocarpronic acid, cloxyfon, clozalon, CMA, CMMP, CMP, CMU, Kodizime, cholecalciferol, fosthiazate, 8-hydroxyquinoline copper, copper acetate, copper arsenite, copper carbonate, basic, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper silicate, copper sulfate, basic copper sulfate, zinc chromate, clofenamate, murazol, coumaphos, kruserus, coumaphos, rodenticide, methidathion, coumaphos, croton, crot, Thiabendazole, sulcotrione (cumyleron), prosulfuron, thiram, cuprous oxide, curcumenol, CVMP, cyanamide, cyanazine, cyanophos, cyanogen, cyanophos, pyraclonil, flufenofos, cyantraniliprole, cyanuric acid, cyazofamid, span, cyclanilide, cyclamate, cyhalothrin, cyhaloanilide, cyhalofop, temon, cyclosulfometuron, cycloxaprid, cyhalothrin, cyhalodiamide, cyhalofop, cyhalothrin, cyhexatin, acarine, cyazofamid, cyanamide, cyhalothrin, cyazofamid, cyhalothrin, fenpyrafos, dodine, metsulfuron, thatch, daminozide, pyridaben, dazomet, DBCP, d-camphor, DCB, DCIP, DCPA (Japan), DCPA (USA), DCPTA, DCU, DDD, DDPP, DDT, DDVP, imicarb, decamethrin, deltamethrin (decamethrin), carbofuran, deet, deoxyacetic acid, diquat (deiquat), isobutamid, epoxythion, deltamethrin (deltamethrin), tianopos, demeton-S, demeton-methyl, demeton-O, methyl-O, demeton-S, methyl-S-sulfone, demeton-S-methanesulfonic acid, DEP, bioallethrin, rotenone, betamethamphetamol, desmetryn (desmethyl), thiothrin, thion, thio, Chlorophosphine, chloroformithion, dichlormate, didymite, diamminephos, dicamba, diatomaceous earth (diatomaceous earth), diatomaceous earth (diatomamite), diazinon, dibromophosphorus, dibutyl phthalate, anthelmintic, dicamba, isochlorophos, dichlobenil, dichlorobenzothiazole (dichlorobentazox), dichlofenphos, benazol, dichloronaphthoquinone, chlorsulfuron, diflubenzuron, fluorenes carboxylate, dichlorofluorenol (dichlorflunol), benzylamine, dichloropropyleneamine, dichloromethane, dichlorophenol, dichloropropionic acid-P, dichlorvos, dichlorzolin (dichlorzolin), sclerotiniozoline (dichlorzoline), benzylchlorotriazole, dichlorosimol, diclofenamic acid, diclofenapyr, chlomethylamine, dichloromethionine, dichlorfenamate, dichlorfenaminosulf, dichlorphenazone, dichlorvone, diclozoline, diclofenapyr-P, diclofen, dimethomon, dieldrin, dichlofen, diethylentrazon, glycyrrhizin, acitreion, ethion (di ethion), diethofencarb, phosmet, diethylpyrocarbonate, etotal, difenoconazole, bensulide, benralin, amyl, cumarone, benethazine, thiabendazole, flufenzine, difuron, diflufenican, diflufenpyroxim, diflufenuron, dichlormate, dyphylline, dimaderfamite, flumethofenprox, mefenfluros, oxazolone, dimehypol, propyzamide, dimethomorph, flumetofen, dimehypol, dimethomorph, dimethorph, dimethyiphthalate, dimethybride, dimethoxim, pyridaben, dimethomorph, dimethofen, pyridalyl, dimethofen, dimethlike, Dimoxystrobin, diclopyridazine (dimopropyridaz), diazinon, chlordiazuron, fenaminophen, pyrisoxazole, dactylene-M, dinoamine, dinitrophenol, dinoflagon, chlormeprop-4, chlormeprop-6, clodinafop-propargyl, dinofenox, nitryl, nitrol, pentol, dinocap, dinotefuran, terbenol, nitrobutyl, phene, fenthion, dioxacarb, fenamiphos, dioxathion, dipheny (diphacin), diphacinone (diphacinone), benzindone, dichlophenazine (diphenamid), dichlorphenamide (diphenhydramide), diphenylsulfone, diphenylamine, diphenylsulfide, furazonic acid, dimethomorphin, isopropyl, trichlorfon, pimox, dithiopyr, diphenoxylate, dicofol, tetraborate, dimercaptophan, methidathion, thifenthion, pyraclonil, thifenthion, pyraclonil, pyrazofos, thifenthion, pyrazofos, Dimethyldisulfide, diethylcarbaminate, dithiopyr, dacron, biflavine, d-limonene, DMDS, DMPA, DNOC, moroxydine, doxycycline, tannin, phenoxypropargite, dodecylguanidineacetate, silly attractant, doramectin, DPC, diketene, DSMA, d-trans allethrin, d-trans bifenthrin, Dufulin, fenflurophoron, Cyprofron, EBEP, EBP, cadusafos, ecdysterone, clomazone, EDB, EDC, EDDP, kewensan, Liquiritin, emamectin, EMPC, empenthrin, enadenin, endosulfan, endothal, indifos, intestin, trifloxystrobin, enostrobin, enostrobilurin, enoconazole, enestroburin (enoxastrobin), EPN, propiolactone, propiconazole, eplanolide, eprinomectin, fendinium, flutriafol, metosulbutrin, -metoclopramide, -metocloprofenprox, -mefenamate, -etofen, EPTC, metolachloraz, epifenatol, EPTC, dimetachlor, flufenamate, flufenacetrin, flufena, Dichlorcaproamide, bioallethrin, esfenvalerate, ESP, penetryn, ethenosilane, epoxiconazole, etamectin, metiram, ethaboxam, butachlor, flutolanil, ethametsulfuron, ethofencarb, ethephon, thidiazuron, chlordane, imazarb, esfenthiuron, ethiprole, iprovalicarb, benfuresamin, ethofumesate, ethoprophos, profenofos, fluroxypyr, oxypyr, ethoxysulfuron, indester, ethyl formate, ethyl pyrophosphate, ethoxydri, ethyl-DDD, ethylene dibromide, ethylene oxide, ethylicin, 2, 3-dihydroxypropyl mercaptane, mercuric ethyl acetate, mercuric bromide, mercuric chloride, mercuric phosphate, nitrophenol, ETM, etofen, etofenapyr, etofen, etofentrazol, etoxazole, Edulide, etrimfos (etrimfos), etrimfos (etrimphos), eugenol, EXD, fenamiphos, sulfamethoxazole, varroa, fenamidone, fenaminostrobin, fenaminosulf, fenazaquin, fenflurane, fenbutatin oxide, fenclofos, fenclorim, fenobucarb, fenpropathrin, fenfluramine, fenhexamid, fenflurazone, fenpropathrin, fenaminostrobin, fenpropathrin, fenbuconazole, fenbucarb-ethyl, fenbutatin oxide, aldicarb, fenoxycarb, fenoxanil, fenoxaprop-P, isoxaprop-sulfone, fenprophen, fenpicrin, fenpicromazine, fenpropathrin, fenpyrad, fenpyraflufen-P, isoxafen, fenpropathrin, fenpyrad, fenpyrofen, fenpyrad, fenpyroxafen, fenpyrad, fenpropathrin, fenpyroxafen-P, Thiazol-diclofop-methyl, fenflurazon, ethofenprox, thiabendazole, fentin, fentrazamide, fluazifop-methyl, fenflururon-TCA, fenvalerate, ferbamate, feimid, iron phosphate, ferrous sulfate, fipronil, flularazinam, fluazifop-M, flazasulfuron-methyl, flocou-methyl, flupiride, florasulam, fluroxypyr, flupirfenim (florylpixamid), flufenamidopropyl, fluazinam (fluzandolizine), flufenoxaprop-ethyl, fluazifop-P, fujim, ipropyr, fluazuron, flutriafol, fluketosulfuron, fluazifop, flufenoxuron, flucarbazide, cyfluthrin, fenprophen, fenflurazon, flufenin, flufenacet, flufen, flufenacet, Triflourethe, flupyridaphenthrin, flutenzine, flubenazenil, fluhexifene, fluindazinam (fluidapyr), flumethrin, flutolanil, flumetralin, flumetsulam, flumethazine, flumiclorac-pentyl, flumiprazole, flumorph, fluometuron, fluopicolide, fluopyram (fluopioside), fluopyram, flutriafol, Zeolite, fluoroacetamide, fluoroacetic acid, flutolmeturon, pyraflufen-ethyl, fluoroxafen-ethyl, carfenflurazone, fluroxypyr, fluthiazone, triflumuron, trifluofen-ethyl, oxapyr-ethyl (fluoxaprin), primisulfuron, flufenpyr-ethyl, flurtamone, flutriafamone, fluazinam-ethyl, fluridon-ethyl, fluazinone, fluazinauplon, fluquinacrine, fluazion, fluazinam, flufenadine, pyriminobac, fluorosulfonamide, flurtamone, phenmedipham, sulfluramid, flutenzine, azimilic acid, flufenacet, flutinib, fudocodin, phenformin, fluvalinate, fluxamide, fluxapyroxamide, flufenapyr, folpet, fomesafen, disulfoton, primisulfuron, flupyrazouron, formaldehyde, vamiprid, anguo, carboxim, foscarnet, fenthion, fosaprazathion, fosthiazate, butathifenphos, flurazophos, flurazofamide, fluroxypyr, fluvalinate, fluvalicarb, flutriafol (furumil), fluoroacetamide, fluoronapropamide, flutolanil, furbenuron, glycolaldehyde, furalaxyl, furametpyr, furethrin, furametpyr, furbenfuracarb, furazolidone, fur, Fenpyrad, furbensulfuron, furbenuron, gamma-BHC, gamma-cyhalothrin, gamma-HCH, cyromazine, gibberellic acid, gibberellin A3, lasiosphaera, calamine (glifter), calamine (glator), aldochlorose, glufosinate-P, orchidine, glyoxime, glyphosate, gossypodium, a cotton bollworm attractant, a limonene-trap, griseofulvin, guanoxetine, biguanide salts, quinolinylacrylate, halauxifen, benazolin, chlorfenapyr, fluoronitrosulfamide, halosulfuron, flurazinam, haloxyfop-P, haloxyfop-R, HCA, HCB, HCH, hexametaphosphate, HeOD, heptachlor, halothrin, zepine, amethoxime, herbicidin, hexamycin, hexaflumetsulam, hexachlorothion (chlor-acetone), chlorohexythrophos, chlorohexythiazox, chlorfenapyr, hexafos, Hexachloroprene, hexachlorobenzene (hexachlorophene), fexofenadine, hexaflumuron, hexafluramine, potassium hexafluoroarsenate, hexapetide, hexazinone, hexythethion, hexythiazox, HHDN, jojobe, homobrassinolide, cycloxaprid, dicyclanil (Huangachong), asulam, cyclazon, hydramethylconazole, hydramethylxafen, hydrargyrum, hydrabam, hydrogen cyanide, methoprene, hymexazol, prodigy, IAA, IBA, IBP, licarbazepine, imiben, imazamox, imazethapyr, imazapyr, imazaquin, imazasulfuron, imibenconazole, neonicophos, imidacloprid, clindamine, kexin, prallethrin, imazapine, clodinafzethazone, indomethabenzuron, indomethazine, indoxacarb, cumquat, thifenclofenclofenclofenpyr, furam, indomethabenzuron, indomethacin, iodophorum, iodonium, iodophorum, youfasuron, iobenonitrile, Oxazin, IPC, ipconazole, Ifencarbazone, efaconazole, Iflufenoquin, propylclofenasone, iprodione, Valicarb, propadine, isocorydine, breprenol, IPSP, IPX, clozapine, imazasone, carboclorim, buticamine, isocarbophos, isoxadifen, isocycloseram, isoethazine, isoxadifen, isoxaflutole, isofluroxypyr, isoxadifen, isofenpyrad, isoxadifen, isoxaflutole, isofenthiuron, isofenpyrazamide, isoxadifenoconazole, isoxadifenox, isoxadifen, isoxadifenox, isoxadifenoconazole, iso, Isoxazole, speransphol (izopamfos), speransphol (izopamphos), japanese scarab attractant, prallethrin, jasminum I, jasminum II, jasmonic acid, azone, methamphos, mefenamate, benoxate, benoxaden, sethoxydim, jinggangmycin A, iodothion, juvenile hormone I, juvenile hormone II, juvenile hormone III, kadethrin, kappa-bifenthrin, kappa-tefluthrin, carbendazim, calathidin, kasugamycin, kefir, clindamycin, dioxolane, clomazone, diatomaceous earth (kiesguhr), activin, enyne, benalaxyl, clarithrone, quinoxyne, lactofen, lambda-cyhalothrin, lanotrione (lancotricone), raloxil, plumbagin, leprosyn, bromophenophos, biphenylingate (libenzingyl), thifenthion, triazophos, trinitron, trinitrogen, bensultrinitrogen, benazolidone, bensultrinitrogen, benazol, Noctuid, lotilanid, lufenuron, cyhalodiamide (lupulin), clofenuron, cyhalodiamide (lupuqiingchongxianan), dichlorvophos (lupixancaolin), clopicoxystrobin, meperfluthrin (lvfumijvzhi), clofenphos, fosthiazate, M-74, M-81, MAA, magnesium phosphide, malathion (malathion), malehydrazide, propionitrile, maltodextrin, MAMA, mancozeb, mandelin, mandipropamid, mannain, triazophos, MCP, MCC, MCPA-thioethyl, MCPB, MCPP, fenpropidin, triazophos, methidathion, meclofenphos, meclofenoac, meclofenpyr-P, meclofenamic acid-P, fenpyr-P, lurex, dimethomorph, fenapyr, fenpyrazamide, mefenapyr, mefenoxanil, mefenamic acid, mefenapyr, dimemoroxydine, MEMC, chlorfenapyr, MEP, mepanipyrim, meperfluthrin, mefenoxate, dinocap, meprobamate, mephos, fenthion, thiothion (mercaptophs) thiol, malathion (mercaptothrione), mercuric chloride, mercuric oxide, mercurous chloride, phosphorous defolianate, phosphorous oxydisulfide, atrazine, mesosulfuron-methyl, mesotrione, mesulfen (mesufen), phosphorus methosufen (mesufofos), methiofen (mesulphen), metacresol, cyflufen, metalaxyl-M, metalaxyl, metam, metamifop-ethyl, metam-methyl, metoclopramide, pyrazosulfuron-methyl, metoclopramide, metocloprofen, metoclopramide, metoclopr, Metsulfuron, methidathion, methiocarb, fenamidone, methimazasulfuron, methidathion, methidazolin, methicillin, ethoprophos, metolcarb, cinolone, nabumetone, meclofenoxate, mechlorethan, germyl, fenclozine, butyl quinacrine, methothrin, methoxychlor, methomyl, methoxyfenozide, tralkoxydim, methyl triazoxide, methyl bromide, methyl eugenol, methyl iodide, methyl isothiocyanate, methyl parathion, methyl ethyl phosphate, methyl chloroform, methyl dithiocarbamate, methimauron, methylene chloride, methyl isoxathion, methyl fenthion, methyl mercurobenzoate, cyguanomethyl, meclofenoxate, methyl neodecanoamine, fenitrothion, bafop, methiazolin, metiram, zineb, pyrron, bromuron, metofluthrin, metolachlor, mechlor, mechlorethan, mec, Metolcarb, tribenuron-methyl, metominostrobin, metoclopramide, fenaminostrobin, metrafenone, fenaminostrobin, metrazine, trichlorfon, tiadinil, metsulfuron, metytetraprole, metoclopramide, trebucarb, mieshuwei (miechuwei), fenaminostrobin, methomyl (miewen juzhi), milbemectin, milbeoxime, metiram, triafamone (miman), propanifop, MIPC, mirex, MNAF, agarol, pradimidine, monosultap, monoflufenapyr, heptanoyl, texauron (monomormonuron), monomethylamidine, monochloroacetic acid, monocrotophos, chlorsulfuron, monosultap (monomethylopo), sulferon, sulfometuron, monosultap (monosultap), monuron, meturon-methyl, meturon-MPvavaglim, mefentraz, MTcozam, metocloprid, metoclopramide, MCT, metoclopramide, NAA, NAAm, Nayipu, naphalanophos, naled, naphthalene, naphthylacetamide, naphthalic anhydride, naprophos, naphthyloxyacetic acid, naphthylacetic acid, naphthylindan-1, 3-dione, naphthyloxyacetic acid, naphthylpropylamine, alachlor, napropamide-M, napropamide, natamycin, NBPOS, nebupromale (neburea), nebuproman (neburon), endrin, quinoa, parathion (chlorofos), aclonifen, niclosamide, boscalid, nicosulfuron, nicotine sulfate, fomesafen, nikkomycin, NIP, fluorochloroachlor, triclosan (nipyralofen), nitenpyrafen, nitroethylthiazole, sulindac, chloropyridine, pennyroyal, aclonifen, triflumuron, nitrostyrene, ipranolone, triadimenol, norflurazon, fenfluridone, sumatran, fenfluridone, thiuron, fenfluridone, thiuron, cyhalouron, fenflurandrin, fenflurandrone, NPA, NPN (N) and N, NPN, N (N) and N (, OCH, octachlorodipropyl ether, octreotide, o-dichlorobenzene, furamide, omethoate, o-phenylphenol, prosulfocarb, efurol, triclopyr, o-dichlorobenzene, orthosulfamuron, oxcarbazone, orysastrobin, oryzalin, osthol (osthol), Ostemone (ostrone), oweringtoni (ovatron), clofenpropite, oxadiargyl, oxadiazon, oubest, oxamate, oryzal, pyridaben (oxapyrazon), oxazosulfuron, olzilin, oxaziclomefone, oxazosulf (oxazosulfyl), oxine-copter (oxapine-copper), oxine-Cu, esolinic acid, oximidazole, oxabetel, mephos-fosinate, isoxathion, sulfothion, oxyphos, oxyphenbutazone, PAC, paclobutrazol, miticide, paclobutrabeclomezine, fenamic, fenaminoxidin, fenamic, fenaminoxidin, oxymatrizine, fenamic, fenaminoxidin, fenamic, allethrin, PAP, p-dichlorobenzene, p-fluometuron, paraquat, parathion, methyl parathion, pirflufen, paris green, PCNB, PCP-sodium, p-dichlorobenzene, PDJ, Kelamon, fenaminophen, corhodin, pelargonic acid, Pingchun, Biclone, pendimethalin, triclosan, penflufen, dimeflufen, Pinctaluron, pennisetum, pentachlorophenol, pentachlorophenyl laurate, penflufen, penthiopyrad, pencyhalothrin, pentoxazone, mirex, fomesafen, permethrin, dimethenamid, phoxim, phenan, diclofen, dimeglum, bisethylcarb (phn tacarbebebebel), gossypen, fenthion, phenmedipham, thiuron, thifenthion, fenpropathrin, phenthol, phenthoate, phenthol, hydrargyrum chloride, thimerosal, flufen, flufenicol, fluazurin, benfurazolate, fluazurin, benfurazolite, benfurazolidone, benflurazon, Phenylmercuric derivatives of catechol, phenylmercuric nitrate, phenylmercuric salicylate, phorate, phosphamidon, phosmet (phosazetim), phosmet, phenthoate (phosmet), phosmet (phosazetin), triphosphatin, chlorophosphophos, phenmethyl (phosethyl), thiocyclophos, glycothion, phosmet, parathion, phosphamide, phosphane, glufosinate, foscarb, phosphorus, triphosphatin, phoxim, methyl phoxim, tetrachlorophthalide, phthalein (phthalein), phthalein (phthalphos), pyrethrolops, plaspilanta, picbambushia, pethidine, picloram, flupyrazachlor, picoxystrobin, pimaricin, carvone, pinoxaden, piperazine, piperonyl butoxide, piperonyl cyclohexenone, piperonyl, mepiquat (meprobamate), methylamine, piperonyl butoxide, mepiquat, benate, mepiquat, mepiqu, Metolac, methimazone, triclocarban, PMA, PMP, polybutene, polycarbamate, toxaphene, polyethoxyquinoline, polyoxin D, polyoxin, spinosad, polythiazane, potassium arsenite, potassium azide, potassium cyanate, potassium ethylxanthate, potassium naphthenate, potassium polysulphide, potassium thiocyanate, pp' -DDT, prallethrin, precocene I, precocene II, precocene III, pretilachlor, acephate, primisulfuron, prometryn, propiconazole, prometryn, trifluralin, profenofos, flumetsulam, cyfluthrin, profenofos, propfluthrin, clethodim, insecticidal amine, ganciclazine, prohexadione, jasmone, lufenuron, methiocarb, prometon, prometryn, metryn (metryn), prometryne, metoclopramide, propyzamide, prop, Propamidine, propamocarb, propanil, propaphos, propaquizafop, propargyl, propargite, tetramethrin, prometryn, bamamidophos, anilazine, propidium, propidin, methylzinc napropamide, propisochlor, endosulfan, prosulfuron, clomazone, propsulfuron, propyribac, propoxymnolide, anabolactone, methidathion, prosulfocarb, prosulfuron, ethiofen, thiobencarb, prothioconazole, phosmet, propylbifenthrin, propyzamide, pimelofos, pyrazothion (proxyphosphs), guanamine, psoralen (psoralen), bendazalone (p), pyrazofenox (pyflumetofen), fluflubutamine, pefurazone, pyrazofos, pyrazothion, pyraclonil, pyraflufen-ethyl, pyraflufenpyr-ethyl, pyraclostrobin (pyraclostrobin), pyrazofos-ethyl, pyrazofos (pyrazofos, pyraclostrobin, Flufenim, blumerin, pyrazosulfuron, thiopyrazofos, fenpyrazofos, resmethrin, biperiden I, biperiden II, pyrethrosin, isoproxyphylla, propyribac-sodium, pyribencarb, pyribenzoxim, pyributicarb, clomedic, pyridaben, pyridylchlorometyl, pyridylalcohol, pyridalyl, pyridaphenthion, pyrimethanil, pirimicarb, pyriminostrobin, pyriminostrobilus, pyriminostrobin, pyriminostrobilus, pyrazofos, pyrazosulfuron-methyl, pyriminostrobin, pyrazosulfuron-ethyl, pyriminostrobin, pyrazofos, pyrazosulfuron-ethyl, pyrazosulfuron-p, pyrazosulfuron-ethyl, pyrazosulfuron-p-, Hydroxyquinolinyloethanone, quinalphos, methyl quinalphos, quinacrid, quinoxalinone, quinoxalin, quinofumelin, chlorfenapyr, chloramphetamine, fenprophos, fenoxaprop, quinalphos, quizalofop-P, anophelate, fenbixidin, imidazozole, ioxysalamine, R-dactyline, haloprid, diquat, Renaliron, coccinella rubra attractant, pyrethrum, thiocyanobenzamide, rhodojaponin III, virazole, rimsulfuron, flufiprole (rizazole), R-metalaxyl, thiocyananilide (rod thithanil), pyralid, rotenone, ryanodine, unitrine, saflufenuron, thiflusilatran, salicylanilide, silafluofen, fenprox, tranexamin, tranilide, sarafloxacin, silate, silatranexaminatum, silate, silafluoxyfen, quinate, quinalphos, S, bioas, sarfluthrin, quinate, quinalphos, bensulam, bensul, Eleutheroside, terbuthylazine, metolachlor, sedaxane, selamectin, amitraz, chrysanthemum indicum, sesamolin, cyprodin, sifenacet, sevin, phosmet, bialaphos (shuangjianancholin), S-methoprene, siduron, transfluthrin (sifunjvzhi), trap ring, silfenfen, silicon mosil, silica aerogel, silica gel, silthiopham (silthiofam), silthiopham (silthiopham), silthiopham (silthiopha), triclosan, simetryn, simeconazole, simatong, simetryn (simetryn), simetryne (simetryne), imazaquin (silthiopham), S-enyne ester, slaked lime, SMA, S-mechloraz, S-sodium isopropanolate, sodium chlorite, sodium arsenite, sodium arsenical, sodium chlorate, sodium hexafluoroacetate, sodium benzoate, sodium orthochlorophenoxylate, sodium benzoate, sodium orthobenzol, sodium benzoate, sodium hexafluorobenzoate, sodium benzoate, sodium, Pentachlorophenol sodium oxide, sodium polysulfide, sodium fluorosilicate, sodium thiocarbonate, sodium thiocyanate, benzalkonium chloride, thiophosphoryl, spinetoram, cinofenozide, spirodiclofen, spiromesifen, spirotetramat, sethoxydim, streptomycin, brucine, folpet-methyl-induced alcohol, sulfophenyl-uron, sulcotrione, sulfydryl, sulfentrazone, sulfenoac, sulfluramid, sulfosulfuron, sulfodiazuron, sulfosulfuron, sulfometuron, sulfophos, sulfometuron, sulfotep, sulfoxaflor, sulfoxides, sulfoxidon, sulfur, sulfuric acid, sulfuryl fluoride, oxsul, sulfophos, thiopropaphos, pennisone, imazamethabenzuron, tau-fluvalinate, carepenen, TBTO, TBZ, TCA, tcbutachlor, TCNB, tcfentebufenpyrad, tebufenpyrad, quinupron (quinupron), quinupron, tezine, tebucarb, tebuconazole, quinalphos, tebuconazole, quin, Grazing amine, buthiuron, kukukuro, tetrachloronitrobenzene, thiram, dicoforsone, difenox, tefururon, temefos, temephos, thion, aldicarb, TEPP, tepraloxydim, topramezone (tepraloxyim), topramezone (teproxydim), cyclopentene, terbacil, menhadione, terbacil, metolachlor, terbuthylazine, budding, terbutryn, quinupristine, terramycin (terramicin), oxytetracycline (terramycin), terbromycin, specularine, tetrafluoropyroroline (tefluprolipolomet), tetrachlorochlorantranilide, tetrachloroethane, sethoxydim, tetrachlor, trichlorosulfone, tetradiful (tetradiferul), tetrafluorolong, tetramin, fenpropathrin, fluocyanamide, thallium sulfate, thallium, thifluthrin, theta-fenvalerate, theta-tetramethrin, thifluthrin, theta-sultamide, theta-propathrin, theta-thifluthrin, theta-sultrine, theta-thifluthrin, thifluthri, Thiacloprid, thiadiazine, thiadifluoride, thiamethoxam, thifensulfuron-methyl, thifenpropionitrile, thifluuron (thiazafluron), thifluuron (thiazfluron), thiaketone, thiabendazole, benzothiophen, thiacetonitrile, thiadiazolidine, thidiazuron, thiencarbazone-methyl, thifensulfuron-methyl, cyflufenacet, thimerosal, phorate, thiobencarb, carbosulfan, thiochlorobenzimide, thiochlorophene (thiochromethidium), thiocyandinitrobenzene (thiocyanatodinobenezene), thiocyclam, thiodan, copper, thiochroman, monocarb (thiocarocarb), monocarb (thiochromox), thiochroman (thiochromox), thiofenflurane, thifenthion, thifenuron, thifenthion, thifenchlorambum, thifenpyrone, thifenpyroxim, thifenthion, tecorim (tioclorim), texafen (tioxazafen), thiocyanobenzamide, clemizoxime, TMTD, methyldiocordon, tolfenpyrad, tolprocarb (tolprocarb), topiramate (tolpyrate), tolfluanid, mefenoxam, phenylmercuric acetate, tomalin (tomarin), topyrazole, toxaphene, TPN, tralkoxydim, bromocypermethrin, tralomethrin, pyrronitrile, bifenthrin, resmethrin, sterile, triacontanol, triton, triafamone, triallate (triallate), fenbuconazole, imazalil, fenazalil, pyrithion, triasulfuron, triazamate, triazophos (triazothiazole), triazophos, triafolon, fenapyr, triclopyr, triclop, Trichlorfon, isopsorrel phosphorus-3, toxic phosphine (trichlorfon), toxic phosphine (trichlorfone), trichlorotrinitrobenzene (trichlortrinitrobenzenes), trichlorfon (trichlorphon), triclopyr, triclopyricarb, tricresyl, tricyclazole, tricyclohexyltin hydroxide, sildenafil, imazachlor, fluazid, snail, triclopyr, trifluroxazine, trifloxysulfuron, trifluralin, trifolium, trifoliate, trifluralin, cyrfx, trifoliate, trifolium, trix, trimethacin, triloban, trimethacone, metamifor, triton, trinexapac-ethyl, fentin, methoprene, flutriafolon, flutolanil, tebuconazole, flutriafol, tebuconazole, flutria, tebuconazole, flutria, flutriafol, tebuconazole, te, Virucin A, propamocarb, isoxadone, aphidicol, imazamide, fannpro, imazamox, metribuzin, metocloprid, vitamin D3, warfarin, nitrobenfop, xinjun, alkene oxime amine, xiwojunzhi (xiwojunzhi), XMC, xylem, xylenol, methiocarb, triticonazole (xymezole), bromate, cyanamid, zeatin, and booster amine, synergistic phosphorus (zengxiaolin), zeta-cypermethrin, zinc naphthenate, zinc phosphide, zinc thiazole (zinc thiazole), zinc thiazole (zinc thiophene), zinc trischlorophenol (zinc trichlorophenoxide), zinc yimp, ziram, zilaphos, warfarin, sedamide, pyraclostrobin (zuoanjunzhi), cafenstrole (zuocaan), pyraclostrobin (zuojunzhi), flumeturon, alpha-chlorohydrin, alpha-ecdysone, alpha-mutilurin, alpha-naphthylacetic acid, ethyl beta-ecdysone;
(2) the following molecules in table a:
as used in this disclosure, each of the above is an active ingredient. For more information, see "the collective of Pesticide common names" (located in alanwood, net) and the "Pesticide Manual" (located in various versions, including online versions, of bcpcdata.
Particularly preferred choices for the active ingredient are 1, 3-dichloropropene, chlorantraniliprole, chlorpyrifos, hexaflumuron, methomyl, methoxyfenozide, novaluron, oxamyl, spinetoram, spinosad, sulfoxaflor and trifluoropyrimidine (hereinafter "AIGA-2").
In addition, other particularly preferred choices for the active ingredient are acequinoid, acetamiprid, acetofenapyr, abamectin, oryzanol-methyl, bifenazate, bifenthrin, carbaryl, carbofuran, chlorfenapyr, chlorfluazuron, chromafenozide, clothianidin, cyfluthrin, cypermethrin, deltamethrin, diafenthiuron, emamectin benzoate, endosulfan, esfenvalerate, ethiprole, etoxazole, fipronil, flonicamid, pyriminostrobin, gamma-cyhalothrin, chlorfenapyr, indoxacarb, lambda-cyhalothrin, lufenuron, malathion, methomyl, flucarbazide, permethrin, pyridalyl, pyriproxyfen, spirodiclofen, hydrazide, thiacloprid, thiamethoxam, thiodicarb, tolfenpyrad, and zeta-cypermethrin (hereinafter "AIGA-3").
The term "alkenyl" means an acyclic, unsaturated (at least one carbon-carbon double bond), branched or straight chain substituent consisting of carbon and hydrogen, such as vinyl, allyl, butenyl, pentenyl, and hexenyl.
The term "alkenyloxy" means an alkenyl group further consisting of carbon-oxygen single bonds, such as allyloxy, butenyloxy, pentenyloxy, hexenyloxy.
The term "alkoxy" means an alkyl group further consisting of a carbon-oxygen single bond, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and tert-butoxy.
The term "alkyl" means an acyclic, saturated, branched, or straight chain substituent consisting of carbon and hydrogen, such as methyl, ethyl, propyl, isopropyl, butyl, and tert-butyl.
The term "alkynyl" means an acyclic, unsaturated (at least one carbon-carbon triple bond), branched or straight chain substituent consisting of carbon and hydrogen, such as ethynyl, propargyl, butynyl, and pentynyl.
The term "alkynyloxy" means an alkynyl group further consisting of carbon-oxygen single bonds, such as pentynyloxy, hexynyloxy, heptynyloxy, and octynyloxy.
The term "aryl" means a cyclic aromatic substituent consisting of hydrogen and carbon, such as phenyl, naphthyl, and biphenyl.
The term "biological pesticide" means a microbial type biological pest control agent that is typically applied in a similar manner to chemical pesticides. Typically, they are bacterial control agents, but there are also examples of fungal control agents, including Trichoderma spp and Erysiphe cichoracearum (Ampelomyces quisqualis). One well-known example of a bioticidal or pesticidal agent is a bacterial disease of the genus Bacillus (Bacillus), Lepidoptera, Coleoptera, and Diptera. Biotype pesticides include products based on entomopathogenic fungi (e.g., Metarhizium anisopliae), entomopathogenic nematodes (e.g., Spodoptera exigua (Steinernema feliae)), and entomopathogenic viruses (e.g., Cydia pomonella granulosis virus). Other examples of entomopathogenic organisms include, but are not limited to, baculoviruses, protozoa, and microsporidia. For the avoidance of doubt, a biotype biocide is the active ingredient.
The term "cycloalkenyl" means a monocyclic or polycyclic unsaturated (at least one carbon-carbon double bond) substituent consisting of carbon and hydrogen, such as cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornenyl, bicyclo [2.2.2] octenyl, tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.
The term "cycloalkenyloxy" means a cycloalkenyl group further consisting of carbon-oxygen single bonds, such as cyclobutenyloxy, cyclopentenyloxy, norbornenyloxy, and bicyclo [2.2.2] octenyloxy.
The term "cycloalkyl" means a monocyclic or polycyclic saturated substituent consisting of carbon and hydrogen, such as cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, bicyclo [2.2.2] octyl, and decahydronaphthyl.
The term "cycloalkoxy" means a cycloalkyl group further consisting of carbon-oxygen single bonds, such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, norbornyloxy, and bicyclo [2.2.2] octyloxy.
The term "halo" means fluoro, chloro, bromo, and iodo.
The term "haloalkoxy" means an alkoxy group further consisting of from one to the maximum possible number of identical or different halo groups, such as fluoromethoxy, trifluoromethoxy, 2, 2-difluoropropoxy, chloromethoxy, trichloromethoxy, 1,2, 2-tetrafluoroethoxy, and pentafluoroethoxy.
The term "haloalkyl" means an alkyl group further consisting of one to the maximum possible number of identical or different halo groups, such as fluoromethyl, trifluoromethyl, 2, 2-difluoropropyl, chloromethyl, trichloromethyl, and 1,1,2, 2-tetrafluoroethyl.
The term "heterocyclyl" means a cyclic substituent that may be aromatic, fully saturated, or partially or fully unsaturated, wherein the cyclic structure contains at least one carbon and at least one heteroatom, wherein the heteroatom is nitrogen, sulfur, or oxygen. Examples are:
(1) aromatic heterocyclyl substituents include, but are not limited to, benzofuranyl, benzisothiazolyl, benzisoxazolyl, benzothienyl, benzothiazolyl, benzoxazolyl, cinnolinyl, furanyl, imidazolyl, indazolyl, indolyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl, and triazolyl;
(2) fully saturated heterocyclyl substituents include, but are not limited to, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl, tetrahydrofuranyl, and tetrahydropyranyl;
(3) partially or fully unsaturated heterocyclyl substituents include, but are not limited to, 4, 5-dihydro-isoxazolyl, 4, 5-dihydro-oxazolyl, 4, 5-dihydro-1H-pyrazolyl, 2, 3-dihydro- [1,3,4] -oxadiazolyl, and 1,2,3, 4-tetrahydro-quinolinyl; and is
(4) Additional examples of heterocyclyl groups include the following:
the term "locus" means a habitat, breeding ground, plant, seed, soil, material, or environment through which pests are growing, may grow, or may pass. For example, the locale may be: crops, trees, fruits, cereals, forage species, vines, turf, and/or ornamentals are growing; the place where the livestock live; interior or exterior surfaces of buildings (such as where grains are stored); building materials used in buildings (such as impregnated wood); and the soil surrounding the building.
The phrase "MoA material" means an active ingredient having a mode of action ("MoA") as indicated in IRAC MoA classification v.8.3 (located at IRAC-online.
(1) An acetylcholinesterase (AChE) inhibitor comprising the following active ingredients: sulfocarb, aldicarb, bendiocarb, benfuracarb, carbosulfan, butocarbosulfan, carbaryl, carbofuran, carbosulfan, fenobucarb, varroamidine, furacarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, monocarb, triazamate, oxamyl, XMC, methiocarb, acephate, pirimiphos-methyl, ethoprophos-methyl, thiotep, oxyphos-oxide, clofenphos-methyl, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-methyl, diazinon-P, dichlorvos/DDVP, pirifos-P-dimethoate, methylcrotophos-methyl, disulfoton, ethion-ethyl, fenamiphos-methyl, fenamiphos-P-methyl, fenamiphos-methyl, fosthieron-methyl, pyrazofos, pyraclofos-ethyl, isofenthion, metofos, bensulthion, Methidathion, metofos, monocrotophos, naled, omethoate, oxydrola, oxydisup, parathion, methyl parathion, phenthoate, phorate, phosmet, phosphamidon, phoxim, bromophos, amicarbazone, profenofos, pyrazofos, pyridaphethione, quinalphos, fenitrothion, butylpyrimidine phosphate, parathion, terbufos, sethion, methyl disulfoton, triazophos, trichlorfon, aphidophos, pirimiphos, imiphos-methyl, imo-Haoes (imicyafos), and isopropyl O- (methoxyaminothio-phosphoryl) salicylate.
(2) A GABA-gated chloride channel antagonist comprising the following active ingredients: chlordane, endosulfan, ethiprole and fipronil.
(3) A sodium channel modulator comprising the following active ingredients: cyfluthrin, allethrin, prallethrin, bifenthrin, bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [ (1R) -trans isomer ], deltamethrin, empenthrin [ (EZ) - (1R) -isomer ], esfenvalerate, ethofenprox, fenpropathrin, flucythrinate, flumethrin, tau-fluvalinate, kadethrin, pyrethrin (pyrethrum), benzoxim, phenothrin [ (1R) -trans isomer ], prallethrin, resmethrin, silafluofen, tefluthrin, tetramethrin [ (1R) -isomer ], tetrabromethrin, transfluthrin, permethrin, DDT, and metolachlor.
(4) Nicotinic acetylcholine receptor (nAChR) agonists comprising the following active ingredients
(4A) Acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam
(4B) The amount of nicotine is such that the nicotine,
(4C) the content of the sulfoxaflor is shown in figure,
(4D) fluopyrafuranones, and
(4E) trifluoro-benzene pyrimidine.
(5) A nicotinic acetylcholine receptor (nAChR) allosteric activator comprising the following active ingredients: spinetoram, and spinosyns.
(6) A chloride channel activator comprising the following active ingredients: abamectin, emamectin benzoate, lepimectin, and miticidin.
(7) A juvenile hormone mimic comprising the following active ingredients: hydroprene, methoprene, fenoxycarb, and pyriproxyfen.
(8) Other non-specific (multi-site) inhibitors include the following active ingredients: methyl bromide, chloropicrin, cryolite, sulfuryl fluoride, borax, boric acid, disodium octaborate, sodium borate, sodium metaborate, tartrazine, diazomet, and metam.
(9) A sound responsive organ TRPV channel modulator comprising the following active ingredients: pymetrozine and flupyraquine.
(10) The mite growth inhibitor comprises the following active ingredients: clofentezine, hexythiazox, flutenzine, and etoxazole.
(11) A microbial interference agent for insect midgut membranes, comprising the following active ingredients: bacillus thuringiensis israelensis, bacillus thuringiensis yasha var thuringiensis (b.t.var. aizawai), bacillus thuringiensis kurstaki (b.t.var. kurstaki), bacillus thuringiensis tretinoides (b.t.var. tenebrionensis), and bacillus sphaericus.
(12) An inhibitor of mitochondrial ATP synthase comprising the following active ingredients: tetrachloromite sulfone, propargite, azocyclotin, cyhexatin, fenbutatin oxide, and diafenthiuron.
(13) An uncoupler for generating oxidative phosphorylation by disrupting proton gradient, comprising the following active ingredients: chlorfenapyr, DNOC, and sulfluramid.
(14) A nicotinic acetylcholine receptor (nAChR) channel blocker comprising the following active ingredients: monosultap, badan hydrochloride, thiocyclam, and dimehypo.
(15) A type 0 chitin biosynthesis inhibitor comprising the following active ingredients: bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, noviflumuron, teflubenzuron, and triflumuron.
(16) A type 1 chitin biosynthesis inhibitor comprising the following active ingredients: buprofezin.
(17) A dipteran molting disrupter comprising the following active ingredients: cyromazine.
(18) An ecdysone receptor agonist comprising the following active ingredients: chromafenozide, methoxyfenozide, and tebufenozide.
(19) The octopamine receptor agonist comprises the following active ingredients: amitraz.
(20) A mitochondrial complex III electron transport inhibitor comprising the following active ingredients: hydramethylnon, fenaminoquinone, bifenazate and fluacrypyrim.
(21) Mitochondrial complex I electron transport inhibitors comprising the following active ingredients: fenazaquin, fenpyroximate, fluacrypyrim, pyridaben, tebufenpyrad, tolfenpyrad, and rotenone.
(22) A voltage-dependent sodium channel blocker comprising the following active ingredients: indoxacarb and metaflumizone.
(23) Inhibitors of acetyl CoA carboxylase: comprises the following active ingredients: spirodiclofen, spiromesifen, and spirotetramat.
(24) Mitochondrial complex IV electron transport inhibitors comprising the following active ingredients: aluminum phosphide, calcium phosphide, phosphine, zinc phosphide, and cyanide.
(25) Mitochondrial complex II electron transport inhibitors comprising the following active ingredients: cyenopyrafen, cyflumetofen, and diflufenican (pyfluumside).
(28) A ryanodine receptor modulator comprising the following active ingredients: chlorantraniliprole, cyantraniliprole, and flubendiamide.
(29) Sound-reactive organ modulators-undefined target sites comprising the following active ingredients: flonicamid.
Groups 26 and 27 are not assigned in this version of the classification scheme. In addition, there is a group UN containing active ingredients whose mode of action is unknown or uncertain. This group includes the following active ingredients: nimbin, fenpyroximate, fenisobromolate, chlorfenapyr, dicofol, GS-omega/kappa HXTX-Hv1a peptide, lime sulphur, pyridalyl and sulphur.
The term "pest" means an organism that is harmful to humans or human interests (such as crops, food, livestock, etc.), wherein the organism is from the phylum arthropoda, mollusca, or nematode. Specific examples are ants, aphids, bed bugs (bed bugs), beetles, moths, caterpillars, cockroaches, crickets, earwigs, fleas, flies, grasshoppers, maggots, bumblebees, leafhoppers (jassids), leafhoppers (leafhoppers), lice, grasshoppers, maggots, mealworms, moths, bugs, lygus bugs (plantbugs), plant bugs (planthoppers), wasps, scale insects, silverfish, snails, spiders, jumps, stinks, sympodies, termites, thrips, ticks, wasps, white flies and ironworms.
Further examples are pests in the following
(1) There are the subdivision of cheliera (Chelerata), the subdivision of Multipoda (Myriappoda), and the subdivision of Hexapoda (Hexapoda).
(2) Arachnida (Arachnida), Symphyla (Symphyla), and Insecta (Insecta).
(3) Anoplura (Order). A non-exhaustive list of specific genera includes, but is not limited to: blood louse species (Haematopinus spp.), hypochondrium species (Hoplopleura spp.), long jaw louse species (Linoganthus spp.), human louse species (Pediculus spp.), Lepidium species (Polyplex spp.), Diabrotherus species (Polyplex spp.), tuba species (Solenoptes spp.), and New blood louse species (Neohaemattopinins spp.). A non-exhaustive list of specific species includes, but is not limited to: donkey blood lice (Haematopinus asini), pig blood lice (Haematopinus suis), acantho palaestis (Linogathus setosus), sheep jaw lice (Linogathus ovilus), human head lice (Pediculus humanus carpitis), human body lice (Pediculus humanus), and pubic lice (Pthirus pubis).
(4) Coleoptera (Order Coleoptera). A non-exhaustive list of specific genera includes, but is not limited to: tridentate pissodes species (Acanthoscelides spp.), Strobilantus species (Agriotes spp.), floricoverus species (Antonomus spp.), Meconopsis species (Apion spp.), Stephania species (Apogonia spp.), elongated cerasus species (Araceae spp.), Gualospora species (Aulacophora spp.), Mucuna species (Bruchus spp.), Calathea species (Ceronas spp.), Douglas species (Ceratospora spp.), Ceratophyllus species (Ceratospora spp.), Diothrix spp., Diothyrium species (Colaspen spp.), Puccinum species (Ceratophys spp.), Dioth species (Ceratophys spp.), Diothyrium species (Heterophycus spp.), Ceratophyllus species (Heterophycus spp.), Ceratophycus spp.), Ceratophyllus species (Heterophycus spp.), Ceratophys species (Heterophys spp.), Ceratophys spp., Heterophys spp., Ceratophys spp.), Ceratophys species (Heterophys spp.), Ceratophys spp., Ceratophys species (Heterophys spp.), Ceratophys spp.), Ceratoptera spp.), Ceratoptera spp., Cerato, The present invention relates to a pharmaceutical composition for treating or preventing a disease or condition associated with a mammal, such as a pissodes species (lycotus spp.), diabrotica species (Megascelis spp.), lucida spp (Meligethes spp.), Mezium spp., fusca species (Niptus spp.), otorhynchophorus species (oxytrophus spp.), short Rhynchophorus species (pantophorus spp.), gilles species (phyllophagasp.), striped diving beetle species (phyllothrix spp.), stringotrys species (phyllothuropternus spp.), root gilles spp.), Rhynchophorus spp., cryptophynopsis spp, rhynohypus spp (Rhynchophorus spp.), or Rhynchophorus spp. A non-exhaustive list of specific species includes, but is not limited to: elephant (Acanthoscelides obtectus), Ceratophyllum album (Agrilus spicatipennis), rice flatworm (Ahasverus advena), black fungus worm (Alphiobius dipterinus), Anoplophora glabrata (Anoplophora glabripennis), cotton boll weevil (Anthonomonus grandis), bark beetle (Anthresholtzia barbadensis), bark beetle (Anthresholtzia variegas), bark beetle (Athenanthera), beet elephant (Bothrodes punctatus), pea elephant (Pisum pisorum), Tetrastigma quadrangularis (Calophyllus), yellow beetle (Castanophycus) and yellow beetle (Castanophycus), yellow beetle (Castanophycus) and yellow beetle), yellow beetle (Castanophyceae), yellow beetle (Califolia casticaulis), yellow beetle (Castanophyceae), yellow beetle (Califolia castales), yellow beetle (Califolia casticaceae), yellow beetle (Castanophyceae), yellow beetle (Califolia castales, yellow beetle), yellow beetle (Castanea sativa), yellow beetle (C. latus), yellow beetle (C.sativus), yellow beetle) and yellow beetle (C.sativus), yellow beetle (Castanea), yellow beetle (C.sativus), yellow beetle (C.sativus), yellow rice red beetle (C.sativus), yellow rice beetle (C.sativus), yellow rice red beetle (C.sativus), yellow rice red, Examples of such organisms include corn beetles (Cryptostestus), Paris polyphylla (Cylindrocarpus adspersus), Phillips irpus (Deporausmarginatus), bark beetles (Dermests ladaria), bark beetles (Dermests grandiflora), bark beetles (Dermests macranthus), Mexico bean beetles (Epilachna varivestis), Pectinatus pernici (Euvrillata), Siamese (Fastinus cubae), Siberian (Hylobius), North americana (Hylothus superior bajunulus), alfalfa leaf beetles (Hypera pottica), bark beetles coffee (Hypotenus hamilti), tobacco beetles (Lasidomermaria sericea), potato beetles (Leptothecium), bark beetles (Mepotamotus), yellow rice beetles (Melothuropus lucorula (Melaleuca), yellow rice beetles (Melothria), rice beetles niloticus), yellow rice beetles (Melaleucaria sinensis), rice beetles sinensis (Melaleucaria), rice beetles sinensis (Melales sinensis (Melaleuca), rice beetles sinensis (Melales sinensis), rice beetles (Melaleuca), rice beetles sativus (Melales), rice beetles (Melales), rice corn beetles (Melales) and corn beetles (Melales (Melaleuca), rice corn beetles) and corn beetles (Melales), corn beetles) may, corn beetles, Linear horned beetles (obeea linearis), coconut-borer beetles (oriyces rhinoceros), large-bore sawflies (oryzaephius mercator), sulinan sawflies (oryzaephius surrinamenis), black-horn mud worms (Oulema melanopus), rice negative mud worms (Oulema oryzae), juniper horned beetles (Phyllophaga cuyana), dwarf woodborers (polycaprons stoutiti), japanese red beetles (Popillia japonica), large grain beetles (proteus truncatus), silverfish (rhizomes), striatellus (sinomenius), root nodule elephant (sinomenius), bark beetles (bark beetles) and red beetles (yellow beetles) are included in the same horns), red beetles (yellow beetles) and red beetles (yellow.
(5) From the Order of the Dermaptera (Order Dermaptera). A non-exhaustive list of specific species includes, but is not limited to: forficula auricularia (Forficula auricularia).
(6) The Blattaria Order (Order Blattaria). A non-exhaustive list of specific species includes, but is not limited to: german cockroach (Blattella germanica), american cockroach (Blattella asahinai), oriental cockroach (blattaria orientalis), cherry red cockroach (Blatta lateralis), bicychia woodchuck (parachloro), american cockroach (Periplaneta americana), australian cockroach (Periplaneta australianae), brown cockroach (Periplaneta brunnea), black chest cockroach (Periplaneta fuliginosa), sugarcane cockroach (pyrocatella surrina), and long-rooted cockroach (Periplaneta longipalea).
(7) Diptera (Order Diptera). A non-exhaustive list of specific genera includes, but is not limited to: the present invention relates to a composition for treating insect pests, such as, for example, a plant species of the genus Aedes (Aedes spp.), an agromyzis species (Agromyza spp.), a plant species of the genus trypanosoma (ansetrepha spp.), a plant species of the genus Anopheles (Anopheles spp.), a plant species of the genus Drosophila (Bactrocera spp.), a plant species of the genus cercopicus (ceratitis spp.), a plant species of the genus gadfly (chrysospp.), a plant species of the genus trypanosoma (cochlioma spp.), a plant species of the genus eutrophus (Contarinia p.), a plant species of the genus Culex (Culex spp.), a species of the genus cusylides spp.), a plant species of the genus phyllotophyllotoxin (dasinella spp.), a species of the genus geotrichia species (dermospp spp.), a species of the genus autographolitha (Drosophila spp.), a species of the genus eutrophus (Drosophila sp.), a species of the genus trichophys (Drosophila species (diaphaga spp.), a species of the genus trichophys (diaphaga species of the genus), a species of the genus trichophys (diaphaga species of the genus trichophys spp.), a species of the genus trichophys (diaphaga species of the genus trichophys (diaphag, Gnat (Simulium spp.), Tabanus (Tabanus spp.), and Aedes (Tipula spp.). A non-exhaustive list of specific species includes, but is not limited to: purple alfalfa leaf flies (Agromyzafrontella), Caribbean fruit flies (Anastrepha subspecia), Mexican fruit flies (Anastrepha ludens), West Indian fruit flies (Anastrepha obliqua), melon fruit flies (Bactrocera cucurbitae), Oriental fruit flies (Bactrocera dorsalis), invasive fruit flies (Bactrocera invasions), peach fruit flies (Bactrocera zonata), Mediterranean fruit flies (Ceratotis capitata), leaf gall flies (Dasineura brassica), gray seed flies (Delia platura), abdominal flies (Fannia canicularis), gray leaf flies (Fabricius), enteric fruit flies (Gasterilus intestinestilis), Gracillia cerealis, eastern fruit flies (Oscilaria), housefly larvae (Osnilla), cabbage fly (Ostoria), sheep baby flies (Oscilaria) Cherry fruit fly (Rhagoletis cerasi), apple fruit fly (Rhagoletis pomonella), blueberry fruit fly (Rhagoletis pomonella), Hawthorn fruit fly (Rhagoletis mosellax), Sitodiplosis mosellana (Sinodiplosis mosellana), and stable fly (Stomoxys calcutins).
(8) Hemiptera (Order Hemiptera). A non-exhaustive list of specific genera includes, but is not limited to: the plant species plasmopara coccinella (Adelges spp.), the plasmopara albuginella species (aulacaspira spp.), the plasmopara palustris species (aphrophorasp.), the plasmopara aphid species (Aphis spp.), the Bemisia species (bemis spp.), the plasmopara cerealis species (ceraplasia spp.), the plasmopara hybrida species (chiloasspira spp.), the plasmopara fusca species (chrysophalus spp.), the plasmopara molitor species (cocus spp.), the plasmopara viridis species (empoasca spp.), the american plasmopara eupatula species (Euschistus spp.), the plasmopara ostreae species (lepisapus spp.), the plasmopara nephelinus species (nephelaphus spp.), the plasmopara Nilaparvata species (nephra spp.), the plasmopara nephelinum species (nephelinum spp.), the plasmopara Nilaparvata species (nephelinus spp.), the plasmopara nilapa spp.), the plasmopara Nilaparvata species (nepheline spp.), the plasmopara spp.) Euglena species (piezovirus spp.), euglena species (Planococcus spp.), pink euglena species (Pseudococcus spp.), sinocalamus species (Rhopalosiphum spp.), black armyworm species (Saissetia spp.), myzus variegatus species (Therioaphis spp.), tortoise wax armyworm species (Toumeyellaspp.), orange aphid species (Toxoptera spp.), white louse species (trialeureures spp.), cyrtophila species (triatomatoma spp.) and sagittaria species (Unaspsis spp.). A non-exhaustive list of specific genera includes, but is not limited to: green plant bug (Acrosternum hilare), Piper sativum (Achythipshot pisum), Trionyx brassicae (Aleyrodes proteella), Aleurodicus dispersus (Aleurodicus dispercus), Aleurothrix lutescens (Aleurothrix lutescens), Paralypocladium bicolor (Amrasca bigutulula), Symphytum mangium (Amazoniarum aurantium), Piper faberi (Aphis fabae), Aphis gossypii (Aphis gossypii), Aphis sojae (Aphis virginus), Aphis citri (Aphis virginosa), Aphis citri (Aphis pomi), Aphis solanacearus (Acortex. var. major), Phyllophila (Bectonus major), Pepper, Acetobacter asiaticus (Bectonus), Pepper-nus persicus), Pepper (Bectonus grandis), Pepper (Bacillus valgus), Pepper greenbrix paradise), Pepper (Beisulus flavus grandis (Beisulus), Piper nigra brassica grandis (Beisulus), Piper nigra (Beisraea), Piper nigra indica (Bectonus), Piper nigra indica (Beisulus flavus), Piper nigra) and Piper nigra (Beisulus terreus (Beisulus), Piper nigrum grandis (Beisulus), Piper nigrum grandis (Beisella grandis), Piper nigrum grandis (Beisella grandis), Piper gra (Beisella grandis), Piper gra (Beis, Green belt bugs (Cimex lectularius), ericerus citrifolia (Coccus pseudocerasus), Fatsia farreri (Dagbertus fasciatus), green belly stinkbugs (Dichelospurcatus), Trionyx maydis (Diurapia noxia), Mandarin orange (Diaphorrina citri), Psyllid (Diaphora citri), Psyllid (Dysapphis plantaginea), Trionyx gossypii (Dysdercuus luteulus), Elisa (Edesata), Emerspira minuta (Emdessorula pseudopteris), Empoalella pseudolaris (Empoasca virilis), Aphis palustris (Eriosoma lanugium), grape leafhopper (Euonyx elaphus flavus), Euonyx elata (Euonymus latus), Euonyx fuscus (Helicornia), Euonyx nilapa (Hygrophycus), Euonyx nilapa (Hyssoides laevis), Euonyx sinensis (Hyssopus laevils), Euonymus grandis (Euonymus latus (Hyssoides), Euonymus grandis (Hyssoides), Euonymus grandis (Euonymus), Euonymus grandis (Hyssoides), Euonymus grandis (Euonymus grandis), Euonymus grandis (Euonymus latus) and Euonymus grandis (Euonymus latus), Euonymus grandis (Euonymus grandis), Euonymus grandis (Euonymus latus) and Euonymus latus (Euonymus latus), Euonymus latus (Euonymus latus), Euonymus grandis (Euonymus latus), Euonymus latus grandis), Euonymus latus (Euonymus, Rice (lypocoria oryzae) orius (Leptococcosis oryzae), rice (Leptococcosis oryzae) orius (Leptococcosis varicornis), Lygus hesperus (Lygus heperurus), meadowfoam (Meristotheca) Merlichus (Maconecoccosis hircus), Euphorbia major (Macrostemona aphid), Aphis graminicola (Macrostemona grandis), Aphis citricola (Macrostemona grandis), Adenopsis viridans (Macrostemona), Pectina palmata (Maharanthus fragilis), Triphophora sieboldii (Megacopea), Aphis virescens (Metaplexicola), Phyllophora citrifolia (Parasticta), Phytophus citri (Paracoccus viridis), Phytophus (Phytophus citri), Phytophus citri viridans (Phytophus citri), Phytophus citrina viridans (Phytophus citri), Phytophus citri viridi), Phytophus citri (Phytophus nilapa), Phytophus citri viridi), Phytophus (Phytophus citri), Phytophus citri (Phytophus citri viridi), Phytophus citri (Phytophus citri), Phytophus citri (Phytophus), Phytophus citri (Phytophus citri), Phytophus citri (Phytophus citri viridi), Phytophus citri (Phytophus, Phytophus citri (Neurospora viridi), Phytophus citri (Ne, Plant-related plant bugs (phytosporins relaetivus), gelidid stinkbug (Piezoderus guilidinii), orange stern mealybugs (Planococcus citri), fig stern mealybugs (Planococcus fiscus), tetragonid cebugs (Poecilococcus lineolatus), bilberry bugs (Psalurus vaccinicola), avocado reticulum (Pseudacysysysata perseae), pineapple powder scale (Pseudiococcus breveus), pear round shield shell (Quadraspidistria perniciosa), corn aphid (Rhopalosiphmaidis), grass tube aphid (Rhopalosiphum padi), olive black helmet shell (ISSETINEA), wheat germ (Sarcoporia), white fly (Sinorula grandis), wheat germ (Sinorhiza kura), and wheat germ (Sinorhiza kura).
(9) From the Order Hymenoptera (Order Hymenoptera). A non-exhaustive list of specific genera includes, but is not limited to: the species trichomes sp (acromymex spp.), the species secant americana (Atta spp.), the species bacteruptoria curvata (campotousspp.), the species trichogramma palustre (camplotusspp.), the species trichogramma (diproson spp.), the species trichogramma longum (dolhovenia spp.), the species Formica (Formica spp.), the species trichogramma (monolimulus spp.), the species neodendrolimus (neostigma spp.), the species trichogramma grub (paranatrefena spp.), the species trichogramma (pheromon spp.), the species trichogramma (peyrodon spp.), the species trichogramma (pheromon spp.), the species trichogramma (poid spp.), the species trichogramma (poidomonema spp.), the species trichogramma spp., the species (polimystus spp.), the species trichogramma spp.), the species (trichogramma spp.). A non-exhaustive list of specific species includes, but is not limited to: sinkiang Blastoma belvedere (Athalia rosae), Ant cantoniensis (Atta texana), Aedes cerana (Caliroa cerasi), Apis cerana americana (Cimbex americana), Argentina odorifera (Iridogyrmexhupois), Argentina argentea (Linepithema humulus), Orientia sanguinea (Melifera Scutella), Formica fusca (Monomorium minimus), Solenopsis minuta (Monomorium pharaonis), Neobrevifolia (Neodrinese serotifer), Solenopsis invicta (Solenopsis virica), Solenopsis tropis (Solenopsis geminata), Equisetum hiemalis (Solenopsis molesta), Solenopsis nigra (Solenopsis richteria), Solenopsis radiata (Solenopsis), and Solenopsis obtusena (Watertia).
(10) From the Order Isoptera (Order Isoptera). A non-exhaustive list of specific genera includes, but is not limited to: coptotermes spp, Xenopsylmus spp, Heterotermes spp, Wood termites spp, Meliothecium spp, Ostermes spp, Meliothecium spp, Macrotermes spp, Borago spp, Meliothecium spp, Chrysocodioides spp, Meliothecium spp, Melothrix spp, and Zoothrix spp. A non-exhaustive list of specific species includes, but is not limited to: coptotermes flavipes (Coptotermes flavipes), Coptotermes labialis (Coptotermes sfrenchi), Coptotermes formosanus (Coptotermes formosanus), Coptotermes domestica (Coptotermes sgestroides), Coptotermes lepis (Cryptotermes brevicis), Heterotermes aureus (Heterotermes aureus), Coptotermes albidus (Heterotermes tenuis), Coptotermes albidus (Incisitermes minor), Coptotermes formosanus (Incisitermes mincer), Coptotermes chinensis (Incisitermes snyderi), Coptotermes albidus (Microtermes obliquus), Coptotermes formotermes tenuis (Heterotermes formosanus), Coptotermes formoterus terreus (Oxyttermes formosanus), Coptotermes terreus (Oxytis longitussimus flavipes), Coptotermes dispersus formosanus (Reptis punctatus), Coptotermes flavipes punctiferus spp (Reptis punctatus), Coptotermes seroticus serotinas punctiferus), Coptotermes serotina punctiferus, Reptis serotina, Coptotermes serotina and Reptis serotina (Reptis), Coptotermes serositis serotina terreus (Reptis), Coptotermes seroticus serotina seroticus), Coptoteres seroticus serotina (Reptis), Coptoteres seroticus serotina (Reptis), Coptoteres seroticus.
(11) Lepidoptera (Order Lepidotera). A non-exhaustive list of specific genera includes, but is not limited to: spodoptera species (Adoxophyes spp.), Geotrichum species (Agrotis spp.), Ectropis spp, Ectropis species (Argyroidiana spp.), Spodoptera species (Caococia spp.), Lepidogrypsis species (Caloptilia spp.), Rice borer species (Chilo spp.), Pleurotus species (Chysodeixis spp.), bean flour (Phanerochaeta indica), butterfly species (Colias spp.), Diaphania species (Crambus spp.), Diaphania species (Diaphania spp.), Epimeria species (Diatraea spp.), Spodoptera species (Heliotica spp.), Spodoptera spp.), Spodopterocarpus spp.), Spodoptera species (Heliothis spp.), Spodopterocarpus spp.), Spodopterocarpus spp Rhizoctonia species (Loxagrotis spp.), tenebrio species (malacomonas spp.), glutelinus species (Nemapogon spp.), oriental armyworm species (peridoroma spp.), Plutella species (phyllonospora spp.), mythimna species (pseudolitella spp.), Plutella species (Plutella spp.), phomopsis species (Sesamia spp.), nocturna species (Spoalvelia spp.), petunia species (Synecholla spp.), phomopsis species (Sesamia spp.), Spodoptera species (Spoaoptera spp.), skilforma species (Spoaperoptera spp.), synephora species (Synanthophytum spp.), and Nepalea species (Yponomeuta spp.). A non-exhaustive list of specific species includes, but is not limited to: armyworm (Achaea janata), Trichoplusia ni (Adoxophyesareana), cutworm (Agrotis ipsilon), cotton leaf looper (Alabama argillacea), avocado cunea (Amorbiaceana), navel orange borer (Amylosis transitera), brown spot moth (Anabactodermata fercia), peach kernel moth (Anarsia lineolaris), Jute bridge moth (Anomis sabifera), velvet bean moth (Antarctiagemma mmatis), fruit tree yellow leaf moth (Archiopsis argyrophylla), rose yellow leaf moth (Archiades scoparia), orange-banded leaf moth (Argyroides pterocarpus citri), cabbage looper (Cryptotympana), cabbage moth (Bopyrifera), cabbage looper (Cryptotympana), cabbage looper niponica (Cnodosa), cabbage looper (Cryptotyocapsa), cabbage looper (Cryptotympana), cabbage looper (Bombaria), cabbage looper niponica), cabbage looper (Bombaria), cabbage looper nigella), cabbage looper (Bombaria), moth (Bombaria), cabbage looper nigella (Bombaria), Choristia) moth (Bombaria), Choristia nigella (Bombaria), Choristoneura nigella (Choristoneura), Choristoneura nigella (Chorist, Borer pyricularis (Cydia molesta), Pieris olepis (Cydia nigricana), codling moth (Cydia nigrella), nettle caterpillar (Darna didyma), Diaphania punctiferalis (Diaphanianitia), Diabrotica punctiferalis (Diaphanianitia), Diatraea saccharina (Diatraea saccharalis), Diatraea zea (Diatraea grandiosella), Elephora bodinieri (Eriasinensis), Heliothis virescens (Einernema virtta), Echinella emersoniana (Ectoloma subcondii), Nanmairei zeae (Elasma lutescens), Pieris punctifera (Ephemella maculata), Heliothis zeae (Ephemera lutea), Heliothis zeae (Hepialus armyworm), Heliothis zea punctatus (Heliothis zea), Heliothis zea (Hepialus punctifera), Heliothis zea (Fabricius), Heliothis zea) punctifera (Einerla), Heliothis zea punctifera serotina (Einerla), Heliothis zea (Hepiana), Heliothis zea (Hepialus punctifera), Heliothis zea (Hepiana), Heliothis zea (Hepiana), Helicosa (Helicosa) and Helicosa (Helicosa), Helicosa (Helicosa) variety (Helicosa), Helicosa (Helicosa) and Gracilaria italica (Helicosa), Helicosa) and Helicosa (Helicosa) including Helicosa (Helicosa), Helicosa (Helicosa) including Helicosa (Helicosa), Helicosa (Hel, Cabbage borer (Hellula undalis), tomato moth (Keiferales), yellow leaf borer (Leucinodes orbornianalis), coffee spot looper (Leucoptera offcinalis), leaf miner (Leucoptera flava), leaf miner (Leucoptera subterrata), leaf miner (Leucoptera flava), grape berry leaf roller (Lobesia borna), bean white spine cutworm (Loxagri amphicosta), dance moth (Lymantria dispar), narrow wing leaf miner (Lyonetia collecticola), oil palm knot worm (Mahasena corbia), cabbage looper (Mamestrabasalis), tobacco leaf moth (Manuca seura), bean pod borer (Pimenta), Marylaria (Pimenta), cabbage moth (Piercea), cabbage leaf moth (Piercea), cabbage leaf moth (Piercea), cabbage moth (Piercea), European cabbage leaf moth (Piercea), cabbage leaf moth (Pi, Citrus leaf miners (Phyllocniscierella), leaf miner (Phyllonoryces blaincardella), cabbage butterfly (Pieris rapae), alfalfa green looper (Plastylan scabra), apple bud leaf miner (Platynothera ovata), Indian meal moth (Plodianella interpunctella), diamond back moth (Plutella xylostella), small fruit moth (Polychrosia virginiana), orange fruit moth (Prays endocarpa), olive leaf moth (Prays oleracea), yellow star armyworm (Pseudiplaea unipunctata), soybean ruler leaf moth (Pseudoplusia includens), mint gray leaf moth (Raphissus plusia), yellow stem borer (Sciophylla), yellow rice borer (Semicola), yellow rice borer (Spodoptera), cabbage looper (Spodopteria frugiperda), cabbage looper (Semicola), cabbage looper) moth (Semicola), cabbage looper (Semicola), cabbage looper (Sellera) (Semicola), cabbage looper) moth (Semicola), cabbage looper (Semicola) moth (Semicola), cabbage looper (Semicola) or Semilnacalis), rice stem moth (Semilnacalis), cabbage looper (Semilnacalis), rice leaf looper (Seller (Semilnacalis), rice leaf looper (Sellera), rice leaf moth (Seller (Semicola) or Semilnacalis), Seller (Semilnacalis, Coffee moth (Zeuzera affeae) and the pear moth (Zeuzea pyrina).
(12) From the Order of the Mallophaga (Order Mallophaga). A non-exhaustive list of specific genera includes, but is not limited to: anticillium species (Antiocola spp.), Phthirius species (Bovicola spp.), Phlebopus species (Chelopastosspp.), Phlebopus species (Goniodes spp.), Phthirius species (Menacanthus spp.) and Phthirius species (Trichodectes spp.). A non-exhaustive list of specific species includes, but is not limited to: bovine feather louse (bovicolabovisis), goat-born cow louse (Bovicola caprae), sheep louse (Bovicola ovis), turkey louse (chelopisteelegrearis), horned feather louse (goniodis dispirilis), big angle feather louse (goniodis gigas), chick feather louse (Menacanthus striatanus), chicken feather louse (Menopon gallinea) and psophila canis (trichoderma).
(13) Orthoptera (Order Orthoptera). A non-exhaustive list of specific genera includes, but is not limited to: black locust species (Melanoplus spp.) and Tree species (Pterophylla spp.). A non-exhaustive list of specific species includes, but is not limited to: crickets (Acheta domesticus), Morganella (Anabrus simplex), African mole cricket (Gryllotalpa africana), southern mole cricket (Gryllotalpa australis), Black short mole cricket (Gryllotalpacanthia), European mole cricket (Gryllotalpa hexadactyla), east Asia migratory locust (Loustamitoria), winged hornworm (Microcentim retinerve), desert locust (Schistocerca gregaria) and Sphacelaria furcata (Scudderia furcifera).
(14) From the Order of rodentia (Order Psocoptera). A non-exhaustive list of specific species includes, but is not limited to: colorless booklice (lipocelelis decoloror), louse psyllium (lipocelelis entomophila), Lacsesil aqueous research and Trogium pulsatorium.
(15) The Order Siphonaptera (Order Siphonaptera). A non-exhaustive list of specific species includes, but is not limited to: chicken hornworm (Ceratophyllus gallinarum), black hornworm (Ceratophyllus niger), Ctenocephalides canis (Ctenocephamides canis), Ctenocephalides felis (Ctenocephamides felis), and human fleas (Pulexirritanes).
(16) From the Order Thysanoptera. A non-exhaustive list of specific genera includes, but is not limited to: negrothrips spp (Calithips spp.), Thrips spp (Frankliniella spp.), Thrips spp (Scirothrips spp.), and Thrips spp (Thrips spp.). A non-exhaustive list of specific species includes, but is not limited to: frankliniella bifida (Frankliniella bispinosa), Frankliniella tabescens (Frankliniella fusca), Frankliniella alfalfa (Frankliniella occidentalis), Frankliniella combretana (Frankliniella schultzizylei), Frankliniella orientalis (Frankliniella tricititi), Frankliniella zeae (Frankliniella williamsi), Frankliniella greenthrips (Heliothrips hamorhivialis), Frankliniella abdominis (Rhiphorhithrips cruentus), Frankliniella citri reticulata (Scirothricinus citri), Frankliniella citri (Scirothricinus), Frankliniella tea Thrips dorsalis (Scirothricinis), Frankliniella hammermispora (Thrombinatus), Frankliniella tabescens (Thrombinatus fortunei), Frankliniella tabescens (Frankliniella tabacis), Frankliniella tabaci thistle (Frankliniella tabaci), Frankliniella tabaci (Frankliniella crispa), Frankliniella tabaci (Fra.
(17) From the Thysanura (Order Thysanura). A non-exhaustive list of specific genera includes, but is not limited to, the genera chlamydomonas (Lepisma spp.) and the genera chlamydomonas (Thermobia spp.).
(18) Acarina (Order Acarina). A non-exhaustive list of specific genera includes, but is not limited to: dermatophagoides sp (Aculops spp.), Erysiphe species (Argus spp.), Gemini species (Boophilus spp.), Demodex species (Demodex spp.), Dermacentor spp, epigophytes species (Epimerus spp.), Dermatophagoides sp (Eriophophyes spp.), Harpagophytum species (Ixodes spp.), Isochrysis species (Oligonchus spp.), Pernychus species (Panonychus spp.), Rhipicephalus species (Rhizophus spp.), and Tetranychus species (Tetranychus spp.). A non-exhaustive list of specific species includes, but is not limited to: tracheacarus (Acarapis woododi), spider mites (Acarus sriro), mangifera goiter (Aceria mangifera), tomato acanthophyrus ovatus (Aculops lycopersici), citrus acanthophyrus (Aculus pelekassis), apple acanthophyrus (Aculus schlechleri), winter spotted spider mite (Amblyomma americanum), oval short-hair mite (Brevipalpus pubescens), red short-hair mite (Brevipalpus phoenis), variable-headed ticks (Dermacentorvariabilis), house dust mites (Dermatophagoides pteronyssinus), hornbeam spider mite (Eotetrychus carpinus), Heterophyllus acidilactici (Lipoinicus), cat dornysto (Notoedres cati), spider mite (Oligonychus coffeee), Chinese ilex (Oligonychus ilicis), Onithoides bailii (Ornithronosus bacoti), red spider apple mite (Panychus citri), rust orange mite (Phytocoptruta olera), Tarsonemus polyphylla (Polyphagus demonstrus), red head tick (Rhipicephalus sanguineus), mange (Sarcoptes scabies), Acinetobacter canis (Tegolorum persicum), Tetranychus gossypii (Tetranychus urticae), Tyrophagus longissimus (Tyrophagi) and Varroa destructor (Varrorella destructor).
(19) Spider eyes (Order area). A non-exhaustive list of specific genera includes, but is not limited to: pinna (Loxosceles spp.), Coxifraga (Latrodectus spp.), and Araneis (Atrax spp.). A non-exhaustive list of specific species includes, but is not limited to: 35068a Piperaceae (Loxosceles reclusa), Larodectus major (Latrodectus macrans), and Sydney funnel web spider (Atrax robustus).
(20) Class of complex (Class Symphyla). A non-exhaustive list of specific species includes, but is not limited to: white pine worm (Scutigerella immaculata).
(21) The Subclass Rhamnoidea (Subclas Collembola). A non-exhaustive list of specific species includes, but is not limited to: philippine flemingia chinensis (Bouletiella hortensis), Onychikusetaria juliana (Onychiurus armatus), Onychikuwana (Onychiurus fimetrius), and Philippine flemingia chinensis (Sminthurus viridis).
(22) Phylum Nematoda (Phylum Nematoda). A non-exhaustive list of specific genera includes, but is not limited to: nematodiasis species (Belonolaimus spp.), strongylongyloides species (crigleema spp.), stemphylostyloides species (Ditylenchus spp.), Globodera species (Globodera spp.), cyst nematodiasis species (heterodera spp.), Heterodera species (Hirschmanniella spp.), Necator species (Hoplopolius spp.), nodorhizobium species (Meloidyne spp.), Rhizotylenchus species (Pratoxylenechus spp.) and Endomotongyloides species (Radiopholspp.). A non-exhaustive list of specific species includes, but is not limited to: dirofilaria immitis (Dirofilariae), white potato nematode (Globodera pallida), soybean cyst nematode (Heterodera glycines), corn cyst nematode (Heterodera zeae), Meloidogyne incognita (Meloidogyne incognita), Meloidogyne javanica (Meloidogyne javanica), Onchocerca volvulus (Onchocerca volvulus), Pratylenchus penetrans (Prtylenchus penetrans), Radopholus banana (Opholus similis) and reniform nematode (Rotylenchus reniformis).
(23) The Phylum Mollusca (Phylum Mollusca). A non-exhaustive list of specific species includes, but is not limited to: big snails (Cornu asperasum), slugs of the anilox (Decoceras reticulatum), slugs of the yellow river (Limaxflavus), slugs of the greenhouse (Milax gags) and Pomacea canaliculata (Pomacea canaliculus) are disseminated.
Particularly preferred groups of pests to be controlled are sap-feeding pests. Pests that feed on juice often have piercing and/or sucking mouthparts and feed on the juice of the plant and the internal plant tissue. Examples of sap-feeding pests of particular agricultural interest include, but are not limited to, aphids, leaf hoppers, moths, scale insects, thrips, psyllids, whiteflies, stink bugs and whiteflies. Specific examples of purposes for sap-feeding pests of agricultural interest include, but are not limited to, the order phthiraptera and pediculoptera. Specific examples of hemiptera species of agricultural interest include, but are not limited to, diptera species, cicada species, aphid species, whitefly species, leptosphaeria species, american stinkbug species, lygus spp, tulipirus species, green rice bug species, and aphid of sinonovaculum spp.
Another particularly preferred group of pests to be controlled are chewing pests. Chewing pests typically have mouthpieces that allow them to chew plant tissue including roots, stems, leaves, buds, and reproductive tissue (including but not limited to flowers, fruits, and seeds). Examples of chewing pests of particular agricultural interest include, but are not limited to, caterpillars, beetles, grasshoppers, and locusts. Specific examples of orders of masticating pests that have agricultural interest include, but are not limited to, coleoptera and lepidoptera. Specific examples of coleopteran species of agricultural interest include, but are not limited to, floricoverum species, diabrotica species, phyllotreta species, diabrotica species, cephalospora species, rootyelopsis species, phyllopodium species, gilles species, striped flea species, pterocarpus species, mibewarrious species.
The phrase "pesticidally effective amount" means the amount of a pesticide required to achieve a observable effect on a pest, such as necrosis, death, retardation, prevention, elimination, destruction, or otherwise reducing the presence and/or activity of the pest in the field effect. This may occur when a pest population is expelled from a site, the pest is incapacitated in or around the site, and/or the pest is eradicated in or around the site's action. Of course, a combination of these effects may occur. Generally, the pest population, activity, or both desirably is reduced by more than fifty percent, preferably more than 90 percent, and most preferably more than 99 percent. Typically, a pesticidally effective amount for agricultural purposes is from about 0.0001 to about 5000 grams per hectare, preferably from about 0.0001 to about 500 grams per hectare, and even more preferably from about 0.0001 to about 50 grams per hectare.
Detailed Description
This document discloses molecules of formula one
Wherein:
(A)R1selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(B)R2selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(C)R3selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(D)R4selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(E)R5selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(F)R6is H;
(G)R7selected from the group consisting of: F. cl, and Br;
(H)R8selected from the group consisting of: F. cl, and Br;
(I)R9is H;
(J)Q1selected from the group consisting of O and S;
(K)Q2selected from the group consisting of O and S;
(L)R10selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)1-C3) Alkyl OC (═ O) (C)1-C3) An alkyl group;
(M)R11selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(N)R12selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(O)R13selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(P)R14selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(Q)R15selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Haloalkyl, (C)1-C3) Alkylphenyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl, (C)1-C3) Alkyl OC (═ O) (C)1-C3) Alkyl, and C (═ O) (C)1-C3) An alkyl group;
(R)R16、R17、R18、R19and R20Independently selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、NH2、OH、SF5、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, (C)2-C3) Alkenyl, (C)2-C3) Haloalkenyl, and N (R)21)C(＝O)(R22) Wherein R is16、R17、R18、R19And R20At least one and not more than two of which are N (R)21)C(＝O)(R22)；
(S)R21Selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Haloalkyl, (C)2-C3) Haloalkenyl, (C)1-C3) Alkylphenyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl, (C)1-C3) Alkyl OC (═ O) (C)1-C3) Alkyl, C (═ O) (C)1-C3) Alkyl, and phenyl;
(T)R22selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-aryl, (C)1-C6) alkyl-S (═ O)n-heterocyclyl (C)2-C6) alkenyl-S (═ O)n-(C1-C6) Alkyl, (C)2-C6) alkenyl-S (═ O)n-(C2-C6) Alkenyl, (C)2-C6) alkenyl-S (═ O)n-aryl, (C)2-C6) alkenyl-S (═ O)n-a heterocyclic group,
wherein n is 0, 1, or 2, and
wherein each of said alkyl and alkenyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) Cycloalkyl radicals, and
wherein each of said aryl and heterocyclyl groups may be substituted with one or more substituents selected from the group consisting of: (C)1-C3) Alkyl, F, Cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, aryl, heteroaryl, and heteroaryl,N((C1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) A cycloalkyl group; and is
N-oxides, agriculturally acceptable acid addition salts, salt derivatives, solvates, ester derivatives, crystal polymorphs, isotopes, resolved stereoisomers, tautomers, pro-insecticides (pro-insecticides) of the molecule of formula one,
provided that the following molecules are excluded
Molecule F1299.
The molecule of formula one may exist in different geometric or optical isomers or different tautomeric forms. One or more chiral centers may be present, in which case the molecule of formula one may be present as a pure enantiomer, a mixture of enantiomers, a pure diastereomer, or a mixture of diastereomers. One skilled in the art will appreciate that one stereoisomer may be more active than the other. Individual stereoisomers may be obtained by known selective synthetic procedures, by conventional synthetic procedures using resolved starting materials, or by conventional resolution procedures. Double bonds may be present in the molecule, in which case a compound of formula (la) may be present as a single geometric isomer (cis or trans, E or Z) or as a mixture of geometric isomers (cis and trans, E and Z). Tautomeric centers may be present. The present disclosure encompasses all such isomers, tautomers, and mixtures thereof in all ratios. For clarity, the structures disclosed in this disclosure may be drawn in only one geometric form, but are intended to represent all geometric forms of the molecule.
In one embodiment, the molecule bound to the cyclopropane according to formula one, the carboxamide group and the phenyl group, are in the R, R configuration, as shown below, which is in formula two of a subset of formula one.
In another embodiment, the molecule according to formula one and formula two, wherein R is1Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
In another embodiment, the molecule according to formula one and formula two, wherein R is2Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
In another embodiment, the molecule according to formula one and formula two, wherein R is3Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
In another embodiment, the molecule according to formula one and formula two, wherein R is4Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
In another embodiment, the molecule according to formula one and formula two, wherein R is5Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
In another embodiment, the molecule according to formula one and formula two, wherein R is2、R3And R4Is at least one of SF5。
In another embodiment, the molecule according to formula one and formula two, wherein R is7Is Cl.
In another embodiment, the molecule according to formula one and formula two, wherein R is8Is Cl.
In another embodiment, the molecule according to formula one and formula two, wherein R is7And R8Are not the same substituent.
In another embodiment, the molecule according to formula one and formula two, wherein Q1Is O.
In another embodiment, the molecule according to formula one and formula two, wherein Q2Is O.
In another embodimentA molecule according to formula one and formula two, wherein R10Is H.
In another embodiment, the molecule according to formula one and formula two, wherein R is11Is H.
In another embodiment, the molecule according to formula one and formula two, wherein R is12Selected from the group consisting of: H. f, Cl, CH3And CF3。
In another embodiment, the molecule according to formula one and formula two, wherein R is13Selected from the group consisting of: F. cl, CH3And OCH3。
In another embodiment, the molecule according to formula one and formula two, wherein R is14Selected from the group consisting of: H. f, and Cl.
In another embodiment, the molecule according to formula one and formula two, wherein R is15Is H.
In another embodiment, the molecule according to formula one and formula two, wherein R is16、R18、R19And R20Independently selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、NH2、OH、SF5、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, (C)2-C3) Alkenyl group, and (C)2-C3) Haloalkenyl, and R17Is N (R)21)C(＝O)(R22)。
In another embodiment, the molecule according to formula one and formula two, wherein R is16、R17、R19And R20Independently selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、NH2、OH、SF5、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, (C)2-C3) Alkenyl group, and (C)2-C3) Haloalkenyl, and R18Is N (R)21)C(＝O)(R22)。
In another embodiment, the molecule according to formula one and formula two, wherein R is21Is H.
In another embodiment, the molecule according to formula one and formula two, wherein R is22Selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-aryl, (C)1-C6) alkyl-S (═ O)n-heterocyclyl, wherein n ═ 0, 1, or 2, and wherein each of said alkyl and alkenyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) Cycloalkyl, and wherein each of said aryl and heterocyclyl groups may be substituted with one or more substituents selected from the group consisting of: (C)1-C3) Alkyl, F, Cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) A cycloalkyl group.
In another embodiment, the molecule according to formula one and formula two, wherein R is22Selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-phenyl, (C)1-C6) alkyl-S (═ O)n-pyridinyl, wherein n ═ 0, 1, or 2, and wherein each of said alkyl and alkenyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, and I, and each of themThe phenyl and pyridyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, and I.
In another embodiment, the molecule according to formula one and formula two, wherein:
R1is H;
R2selected from the group consisting of: H. f, Cl, and CF3；
R3Selected from the group consisting of: H. f, and Cl;
R4selected from the group consisting of: H. f, Cl, and CF3；
R5Is H;
R7is Cl;
R8is Cl;
Q1is O;
Q2is O;
R10is H;
R11is H;
R12is H;
R13is Cl;
R14is H;
R15is H;
R16is F;
R17is N (R)21)C(＝O)(R22)；
R18Is F;
R19is H;
R20is H;
R21is H; and is
R22Selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-phenyl, (C)1-C6) alkyl-S (═ O)n-a pyridyl group,
wherein n is 0, 1, or 2;
wherein each of the alkyl, alkenyl, phenyl, and pyridyl groups may be substituted with one or more substituents selected from the group consisting of F and Cl.
In another embodiment, the molecule according to formula one and formula two, wherein:
R1is H;
R2selected from the group consisting of: H. f, Cl, and CF3；
R3Selected from the group consisting of: H. f, and Cl;
R4selected from the group consisting of: H. f, Cl, and CF3；
R5Is H;
R7is Cl;
R8is Cl;
Q1is O;
Q2is O;
R10is H;
R11is H;
R12is H;
R13is Cl;
R14is H;
R15is H;
R16is F;
R17is H;
R18is N (R)21)C(＝O)(R22)；
R19Is H;
R20is H;
R21is H; and is
R22Selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-phenyl, (C)1-C6) alkyl-S (═ O)n-a pyridyl group,
wherein n is 0, 1, or 2;
wherein each of the alkyl, alkenyl, phenyl, and pyridyl groups may be substituted with one or more substituents selected from the group consisting of F and Cl.
In another embodiment, the molecule selected from table 2, preferably a molecule selected from the group consisting of: f2, F3, F4, F5, F6, F7, F8, F9, F10, F11, F12, F13, F14, F15, F16, F17, F18, F19, F22, F23, F24, F25, F26, F27, F28, F29, F30, F31, F32, F33, F34, F35, F37, F39, F42, F44, F45, F46, F47, F48, F49, F50, F51, and F52.
In another embodiment, the molecule is selected from table 2, more preferably from the group consisting of: f3, F5, F6, F10, F12, F13, F14, F15, F16, F17, F18, F19, F23, F27, F28, F29, F31, F32, F37, F39, F46, F47, and F49.
In another embodiment, the molecule selected from table 2, preferably a molecule selected from the group consisting of: f15, F16, F17, F18, F19, F21, F23, F24, F25, F32, F34, and F46.
Preparation of a molecule of formula (III)
Preparation of cyclopropylamides
Cyclopropylamide 1-3 (wherein Q)1Is O, and R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And Q2As previously disclosed) may be prepared by the method disclosed in Heemstra, r.j, et al, U.S. patent 9,781,935B2(WO 2016/168059), and also by the use of amines or amine salts 1-2 (wherein R is10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And Q2Is as previously disclosed) and an activated carboxylic acid 1-1 (wherein A is an activating group, and R is1、R2、R3、R4、R5、R6、R7、R8And R9As previously disclosed) with a base (e.g., triethylamine, diisopropylethylamine, 4-methylmorpholine, sodium bicarbonate, or 4-dimethylaminopyridine) in an anhydrous aprotic solvent (e.g., dichloromethane, tetrahydrofuran, 1, 2-dichloroethane, dimethylformamide, ethyl acetate, or any combination thereof) at a temperature between about 0 ℃ and about 120 ℃ (scheme 1, step a).
Carboxylic acid 1-1 (wherein a is an activating group) which may be an acid halide, such as an acid chloride, acid bromide, or acid fluoride; carboxylic acid esters such as p-nitrophenyl ester, pentafluorophenyl ester, ethyl (hydroxyimino) cyanoacetate, methyl ester, ethyl ester, benzyl ester, N-hydroxysuccinimidyl ester, hydroxybenzotriazol-1-yl ester, or hydroxypyridyltriazol-1-yl ester; o-acylisoureas; an acid anhydride; or a thioester. Acid chlorides can be prepared from the corresponding carboxylic acids by treatment with a dehydrochlorinating reagent (e.g., oxalyl chloride or thionyl chloride) with or without N, N-dimethylformamide. The activated carboxylate 1-1 may be a uronium salt (e.g., 1- [ bis (dimethylamino) methylene)]-1H-1,2, 3-triazolo [4,5-b]Pyridinium 3-oxide Hexafluorophosphate (HATU), O- (benzotriazol-1-yl) -N, N' -tetramethyluronium Hexafluorophosphate (HBTU), or (1-cyano-2-ethoxy-2-oxoethyleneaminooxy) dimethylamino-morpholino-carbonium hexafluorophosphate (COMU)) is prepared in situ from a carboxylic acid. Activated carboxylic acid esters 1-1 can also be prepared in situ from carboxylic acids using phosphonium salts, such as benzotriazol-1-yl-oxytriazolylphosphonium hexafluorophosphate (PyBop). Activated carboxylic acid ester 1-1 can also be prepared in situ from a carboxylic acid using a coupling reagent such as 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, or dicyclohexylcarbodiimide, in the presence of a triazole such as hydroxybenzotriazole monohydrate (HOBt) or 1-hydroxy-7-azabenzotriazole (HOAt). The O-acylisourea can be removedAqueous carbodiimides (e.g., 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide or dicyclohexylcarbodiimide) are prepared. The activated carboxylate 1-1 may also be prepared in situ from a carboxylic acid with a coupling reagent such as 2-chloro-1, 3-dimethylimidazolidinium hexafluorophosphate (CIP) in the presence of a triazole such as 1-hydroxy-7-azabenzotriazole (HOAt). The activated carboxylic ester 1-1 can also be coupled with a coupling reagent (e.g.2, 4, 6-tripropyl-1, 3,5,2,4, 6-trioxane-2, 4, 6-trioxane) Prepared in situ from carboxylic acids in the presence of a base such as pyridine.
An amine or amine salt 1-2 (wherein Q2Is O) is directly treated with a sulfur source (e.g., phosphorus pentasulfide or 2, 4-bis (4-methoxyphenyl) -1,3,2, 4-dithiadiphosphetane 2, 4-disulfide (Lawson's reagent) with or without an additive (e.g., 1,1,1,3,3, 3-hexamethyldisiloxane) in an aprotic solvent selected from tetrahydrofuran, dichloromethane, chloroform, toluene, or pyridine at a temperature of from about 40 ℃ to about 120 ℃ to provide an amine or amine salt 1-2, wherein Q is2Is S.
Scheme 1
Cyclopropylamide 2-3 (wherein Q)2Is O, and R1、R2、R3、R4、R5、R6、R7、R8、R9、Q1、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21And R22As previously disclosed) may be prepared by reacting 2-2 with an amine or amine salt, and 2-1 with an activated carboxylic acid (wherein A is an activating group, and R is1、R2、R3、R4、R5、R6、R7、R8、R9、Q1、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22And Q2As previously disclosed) with a base (e.g., triethylamine, diisopropylethylamine, 4-methylmorpholine, pyridine, sodium bicarbonate, or 4-dimethylaminopyridine) in an anhydrous aprotic solvent (e.g., dichloromethane, tetrahydrofuran, 1, 2-dichloroethane, dimethylformamide, ethyl acetate, or any combination thereof) at a temperature between about 0 ℃ and about 120 ℃ (scheme 2, step a).
The activated carboxylic acid 2-1 may be an acid halide, such as an acid chloride, acid bromide, or acid fluoride; carboxylic acid esters such as p-nitrophenyl ester, pentafluorophenyl ester, ethyl (hydroxyimino) cyanoacetate, methyl ester, ethyl ester, benzyl ester, N-hydroxysuccinimidyl ester, hydroxybenzotriazol-1-yl ester, or hydroxypyridyltriazol-1-yl ester; o-acylisoureas; an acid anhydride; or a thioester. Acid chlorides can be prepared from the corresponding carboxylic acids by using a dehydrochlorinating reagent, such as oxalyl chloride or thionyl chloride. The activated carboxylate 2-1 may be a uronium salt (e.g., 1- [ bis (dimethylamino) methylene)]-1H-1,2, 3-triazolo [4,5-b]Pyridinium 3-oxide Hexafluorophosphate (HATU), O- (benzotriazol-1-yl) -N, N' -tetramethyluronium Hexafluorophosphate (HBTU), or (1-cyano-2-ethoxy-2-oxoethyleneaminooxy) dimethylamino-morpholino-carbonium hexafluorophosphate (COMU)) is prepared in situ from a carboxylic acid. Activated carboxylic acid esters 2-1 can also be prepared in situ from carboxylic acids using phosphonium salts, such as benzotriazol-1-yl-oxytriazolylphosphonium hexafluorophosphate (PyBop). The activated carboxylic acid ester 2-1 can also be prepared in situ from a carboxylic acid using a coupling reagent such as 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, or dicyclohexylcarbodiimide, in the presence of a triazole such as hydroxybenzotriazole monohydrate (HOBt) or 1-hydroxy-7-azabenzotriazole (HOAt). O-acylisoureas can be prepared using a dehydrated carbodiimide (e.g., 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide or dicyclohexylcarbodiimide). Activated carboxylic acid ester 2-1It can also be prepared in situ from carboxylic acids using coupling reagents such as 2-chloro-1, 3-dimethylimidazolidinium hexafluorophosphate (CIP) in the presence of a triazole such as 1-hydroxy-7-azabenzotriazole (HOAt). The activated carboxylic ester 2-1 can also be coupled with a coupling reagent (e.g.2, 4, 6-tripropyl-1, 3,5,2,4, 6-trioxane) Prepared in situ from carboxylic acids in the presence of a base such as pyridine.
Scheme 2
Cyclopropylamide 3-3 (where R is16、R17、R18、R19And R20At least one and not more than two of which are N (R)21)C(＝O)(R22)；Q2Is O, R1、R2、R3、R4、R5、R6、R7、R8、R9、Q1、R10、R11、R12、R13、R14And R15As previously disclosed) may be prepared by reacting an activated carboxylic acid 3-2 (wherein A is an activating group and R is22As previously disclosed) and a base (e.g., triethylamine, diisopropylethylamine, 4-methylmorpholine, 4-dimethylaminopyridine, or pyridine) in an anhydrous aprotic solvent (e.g., dichloromethane, tetrahydrofuran, 1, 2-dichloroethane, N-dimethylformamide, or any combination thereof) at a temperature between about 0 ℃ and about 120 ℃16、R17、R18、R19And R20At least one and not more than two of which are N (R)21)2And R is21Is H; q2Is O, R1、R2、R3、R4、R5、R6、R7、R8、R9、Q1、R10、R11、R12、R13、R14And R15Was prepared as previously disclosed) (scheme 3, step a).
The activated carboxylic acid 3-2 may be an acid halide, such as an acid chloride, acid bromide, acid fluoride, or chloroformate; carboxylic acid esters such as p-nitrophenyl ester, pentafluorophenyl ester, ethyl (hydroxyimino) cyanoacetate, methyl ester, ethyl ester, benzyl ester, N-hydroxysuccinimidyl ester, hydroxybenzotriazol-1-yl ester, or hydroxypyridyltriazol-1-yl ester; o-acylisoureas; an acid anhydride; or a thioester. Acid chlorides can be prepared from the corresponding carboxylic acids by using a dehydrochlorinating reagent, such as oxalyl chloride or thionyl chloride. The activated carboxylate 3-2 may be a uronium salt (e.g., 1- [ bis (dimethylamino) methylene)]-1H-1,2, 3-triazolo [4,5-b]Pyridinium 3-oxide Hexafluorophosphate (HATU), O- (benzotriazol-1-yl) -N, N' -tetramethyluronium Hexafluorophosphate (HBTU), or (1-cyano-2-ethoxy-2-oxoethyleneaminooxy) dimethylamino-morpholino-carbonium hexafluorophosphate (COMU)) is prepared in situ from a carboxylic acid. Activated carboxylic acid esters 3-2 can also be prepared in situ from carboxylic acids using phosphonium salts, such as benzotriazol-1-yl-oxytriazolylphosphonium hexafluorophosphate (PyBop). The activated carboxylic acid ester 3-2 can also be prepared in situ from a carboxylic acid using a coupling reagent such as 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, or dicyclohexylcarbodiimide, in the presence of a triazole such as hydroxybenzotriazole monohydrate (HOBt) or 1-hydroxy-7-azabenzotriazole (HOAt). O-acylisoureas can be prepared using a dehydrated carbodiimide (e.g., 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide or dicyclohexylcarbodiimide). The activated carboxylate 3-2 may also be prepared in situ from a carboxylic acid with a coupling reagent such as 2-chloro-1, 3-dimethylimidazolidinium hexafluorophosphate (CIP) in the presence of a triazole such as 1-hydroxy-7-azabenzotriazole (HOAt). The activated carboxylic acid ester 3-2 can also be coupled with a coupling reagent (e.g. 2,4, 6-tripropyl-1, 3,5,2,4, 6-trioxane) Prepared in situ from carboxylic acids in the presence of a base such as pyridine.
Scheme 3
Cyclopropyl amide 4-2 (wherein two R' s16、R17、R18、R19And R20Is at least one and not more than N (R)21)2And R is21Is H; q2Is O, R1、R2、R3、R4、R5、R6、R7、R8、R9、Q1、R10、R11、R12、R13、R14And R15As previously disclosed) may be prepared by treating 4-1 (where R is a metal (e.g., palladium on carbon) with a metal (e.g., palladium on carbon) in the presence of a reducing agent (e.g., hydrogen) in a solvent (e.g., ethyl acetate) or with a metal (e.g., iron) in the presence of a reducing agent (e.g., ammonium chloride) in a solvent mixture (e.g., methanol and water) at a temperature of about 25 ℃ to about 60 ℃16、R17、R18、R19And R20At least one and not more than two of which are NO2；R1、R2、R3、R4、R5、R6、R7、R8、R9、Q1、R10、R11、R12、R13、R14And R15Was prepared as previously disclosed) (scheme 4, step a).
Alternatively, cyclopropylamide 4-2 (where R is16、R17、R18、R19And R20At least one and not more than two of which are N (R)21)2And R is21Is H; q2Is O, R1、R2、R3、R4、R5、R6、R7、R8、R9、Q1、R10、R11、R12、R13、R14And R15As previously disclosed) may be prepared by using an anhydrous acid solution (e.g.E.g., hydrochloric acid) in 1, 4-dioxane and dichloromethane at a temperature of about 25 deg.C16、R17、R18、R19And R20At least one and not more than two of which are N (R)21)C(＝O)O(C1-C6) Alkyl radical, wherein R21Is H; q2Is O, R1、R2、R3、R4、R5、R6、R7、R8、R9、Q1、R10、R11、R12、R13、R14And R15aWas prepared as previously disclosed) (scheme 4, step b).
Alternatively, cyclopropylamide 4-2 (where R is16、R17、R18、R19And R20At least one and not more than two of which are N (R)21)2And R is21Is H; q2Is O, R1、R2、R3、R4、R5、R6、R7、R8、R9、Q1、R10、R11、R12、R13、R14And R15As previously disclosed) may be prepared by treating 4-1 (where R is a solution of anhydrous acid (e.g., hydrochloric acid) in 1, 4-dioxane and dichloromethane at a temperature of about 25 ℃16、R17、R18、R19And R20At least one and not more than two of which are N (C (═ O) O (C)1-C6) Alkyl radical)2；Q2Is O, R1、R2、R3、R4、R5、R6、R7、R8、R9、Q1、R10、R11、R12、R13、R14And R15Was prepared as previously disclosed) (scheme 4, step c).
Scheme 4
Cyclopropylamide 5-1 (wherein R is16、R17、R18、R19And R20At least one and not more than two of which are N (R)21)C(＝O)(R22) And R is22Containing sulfide) can be oxidized to the corresponding sulfoxide or sulfone 5-2 by treatment with about one equivalent of m-chloroperoxybenzoic acid in a polar aprotic solvent (e.g., dichloroethane) at a temperature between about 0 ℃ to about 50 ℃ (scheme 5, step a). Alternatively, cyclopropylamide 5-1 (where R is R) may be treated with one equivalent of sodium perborate or with two equivalents of sodium perborate (sulfone) in a protic solvent such as acetic acid (sulfoxide)22Containing sulfide) to the corresponding sulfoxide or sulfone. Preferably, the oxidation is carried out at about 40 ℃ to about 100 ℃ using about 1.5 equivalents of sodium perborate to provide a chromatographically separable mixture of sulfoxide and sulfone cyclopropylamide 5-2 (scheme 5, step b). Alternatively, the oxidation of cyclopropylamide 5-1 (containing the sulfide) to the corresponding sulfoxide can be carried out by treatment with about one equivalent of 30% aqueous hydrogen peroxide in a polar protic solvent (e.g., hexafluoropropane) at ambient temperature (scheme 5, step c). Alternatively, the catalyst may be prepared by using about 1 to about 2.5 equivalents
Scheme 5
In another example, the cyclic amino acid R1-1 (wherein R is R1-1) can be prepared by the method of scheme R11、R2、R3、R4、R5、R6、R7、R8And R9As previously disclosed) into its (R, R) and (S, S) enantiomers.
Scheme R1
Wherein: xRIs selected from C1-C4Alkyl or benzyl.
In scheme R1, the (+) -trans racemate of formula R1-1 (i.e., a mixture of the (R, R) and (S, S) enantiomers of trans-2, 2-dichloro-3- (substituted phenyl) cyclopropane-carboxylic acid) is combined with a resolving agent, which is an enantiomeric amine of formula R2-1 or formula R2-2, in a suitable solvent to provide a diastereomeric amine salt of the formula: formula R3-1A or formula R3-1B,
Or of the formula R3-2A or of the formula R3-2B,
The diastereomeric amine salt is selectively crystallized or precipitated from the resulting mixture. The diastereomeric amine salt of formula R3-1A or formula R3-1B, or formula R3-2A or formula R3-2B may then be isolated from the mixture and treated with an acid to provide (1R,3R) -or (1S,3S) -2, 2-dihalo-3- (substituted phenyl) cyclopropanecarboxylic acid of formula R1-2A or formula R1-2B, respectively.
Examples of the invention
These examples are for illustrative purposes and should not be construed as limiting the disclosure to the embodiments disclosed in these examples.
Starting materials, reagents, and solvents obtained from commercial sources were used without further purification. Anhydrous solvent as Sure/SealTMPurchased from Aldrich and used as received. Melting points were obtained on a Thomas HooverUnimelt capillary melting point apparatus or the Optimelt automated melting point System from Stanford Research Systems, and were not corrected. Examples of the use of "room temperature" are carried out in climate control laboratories, with temperatures ranging from about 20 ℃ to about 24 ℃. The molecule is administeredTheir known names are named according to the naming program in ISIS Draw, chemddraw, or ACD Name Pro. If such programs are unable to name molecules, conventional naming conventions are used to name such molecules.1H NMR spectral data in ppm () and recorded at 300, 400, 500, or 600 MHz;13CNMR spectroscopic data in ppm () and recorded at 75, 100 or 150 MHz; and is19F NMR spectral data are in ppm () and recorded at 376MHz unless otherwise stated.
Example 1: preparation of trans-2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropanecarboxylic acid (C1)
The title compound was prepared from trans-1, 2, 3-trichloro-5- (2, 2-dichloro-3- (4-methoxyphenyl) cyclopropyl) benzene (C2) according to the method disclosed in example 1 of heimstra, r.j. et al, U.S. patent 9,781,935B2(WO 2016/168059) and isolated as a yellow powder (1.5 g, 39%):1H NMR(400MHz,CDCl3)7.31(d,J＝0.7Hz,2H),3.40(d,J＝8.2Hz,1H),2.86(d,J＝8.3Hz,1H)；13C NMR(101MHz,CDCl3)171.05,134.55,132.44,131.75,128.89,61.18,39.26,37.14；ESIMS m/z 333([M-H]-)。
example 2: preparation of trans-2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropanecarboxylic acid (C1)
The title compound was prepared according to the procedure disclosed in Heemstra, r.j. et al, us patent 9,781,935B2(WO 2016/168059) in example 96 from trans-2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carbaldehyde (C5) and isolated as a white solid (2.78g, 95%):1H NMR(400MHz,DMSO-d6)13.41(s,1H),7.81(d,J＝0.6Hz,2H),3.62(d,J＝8.6Hz,1H),3.52(d,J＝8.6Hz,1H)；ESIMS m/z 332([M-H]-)。
example 3: preparation of trans-1, 2, 3-trichloro-5- (2, 2-dichloro-3- (4-methoxyphenyl) cyclopropyl) benzene (C2)
The title compound was prepared from (E) -1,2, 3-trichloro-5- (4-methoxystyryl) benzene (C3) and N-benzyl-N, N-diethylethanaminium chloride according to the method disclosed in example 3 of haemstra, r.j. et al, U.S. patent 9,781,935B2(WO 2016/168059) and isolated as a dark foam (4.7g, 100%):1H NMR(400MHz,CDCl3)7.40(d,J＝0.6Hz,2H),7.29-7.22(m,2H),6.96-6.89(m,2H),3.83(s,3H),3.12(d,J＝8.8Hz,1H),3.06(d,J＝8.7Hz,1H)；13C NMR(101MHz,CDCl3)159.46,135.08,134.23,130.91,129.85,129.16,125.42,114.02,64.67,55.32,39.62,38.48。
example 4: (E) preparation of (E) -1,2, 3-trichloro-5- (4-methoxystyryl) benzene (C3)
The title compound was prepared from 3,4, 5-trichlorobenzaldehyde (C4) and diethyl 4-methoxybenzylphosphonate according to the method disclosed in Heemstra, r.j. et al, us patent 9,781,935B2(WO 2016/168059) as example 5, and a white solid was isolated (3.7g, 31%):1H NMR(400MHz,CDCl3)7.49-7.46(m,2H),7.47-7.39(m,2H),7.04(d,J＝16.3Hz,1H),6.93-6.89(m,2H),6.78(d,J＝16.3Hz,1H),3.84(s,3H)；13CNMR(101MHz,CDCl3)159.46,135.08,134.23,130.91,129.85,129.16,125.42,114.02,64.67,55.32,39.62,38.48；EIMS m/z 313([M]+)。
example 5: preparation of 3,4, 5-trichlorobenzaldehyde (C4)
The title compound was prepared from 5-bromo-1, 2, 3-trichlorobenzene according to the procedure disclosed in Heemstra, R.J. et al, U.S. Pat. No. 9,781,935B2(WO 2016/168059) example 10Material and was isolated as a white solid (10: 1 mixture of the title compound with 1,2, 3-trichlorobenzene, 7.96g, 99%):1H NMR(CDCl3)9.91(s,1H),7.88(s,2H)；EIMS m/z 209([M]+)。
example 6: preparation of trans-2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carbaldehyde (C5)
The title compound was prepared from trans-1, 2, 3-trichloro-5- (2, 2-dichloro-3- (diethoxymethyl) cyclopropyl) benzene (C6) according to the procedure disclosed in Heemstra, r.j. et al, us patent 9,781,935B2(WO 2016/168059) example 97 and isolated as a yellow solid (2.8g, 69%):1H NMR(400MHz,CDCl3)9.55(d,J＝3.9Hz,1H),7.30(d,J＝0.7Hz,2H),3.48(dt,J＝8.0,0.8Hz,1H),2.92(dd,J＝7.9,3.9Hz,1H)。
example 7: preparation of trans-1, 2, 3-trichloro-5- (2, 2-dichloro-3- (diethoxymethyl) cyclopropyl) benzene (C6)
The title compound was prepared from (E) -1,2, 3-trichloro-5- (3, 3-diethoxyprop-1-en-1-yl) benzene (C7) according to the method disclosed in Heemstra, r.j. et al, us patent 9,781,935B2(WO 2016/168059) example 98 and isolated as a brown oil (146g, 93%):1H NMR(400MHz,CDCl3)7.29(d,J＝0.7Hz,2H),4.59(d,J＝6.1Hz,1H),3.82-3.54(m,4H),2.75(d,J＝8.5Hz,1H),2.23(dd,J＝8.5,6.1Hz,1H),1.30(t,J＝7.0Hz,3H),1.20(t,J＝7.0Hz,3H)。
example 8: (E) preparation of (E) -1,2, 3-trichloro-5- (3, 3-diethoxyprop-1-en-1-yl) benzene (C7)
According to Heemstra, R.J. et al, U.S. Pat. No. 9,781,935B2(WO 2016/168059)The title compound was prepared from 3,4, 5-trichlorobenzaldehyde according to the procedure disclosed in example 99 and was isolated as an orange oil (40g, 91%):1H NMR(400MHz,CDCl3)7.41(s,2H),6.58(dd,J＝16.1,1.2Hz,1H),6.21(dd,J＝16.1,4.6Hz,1H),5.06(dd,J＝4.7,1.2Hz,1H),3.69(dq,J＝9.3,7.1Hz,2H),3.55(dq,J＝9.5,7.0Hz,2H),1.25(t,J＝7.1Hz,6H)。
example R1: resolution of (1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxylic acid (C8)
The title compound was resolved according to the procedure disclosed in Heemstra, r.j. et al, us patent 9,781,935B2(WO 2016/168059) as example 100 and isolated as a white solid (2g, 29%, 99% ee). The analytical data are in agreement with the racemic acid C1.
Example R4: resolution of racemic trans-2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxylic acid (C9) with (L) -leucinamide to provide (1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxylic acid (C10)
A mixture of (L) -leucinamide (15.6g, 120mmol) and racemic trans-2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxylic acid (C9, prepared according to the method disclosed in example 1 of Heemstra, r.j. et al, U.S. patent 9,781,935B2(WO 2016/168059), 63.4g, 200mmol) in acetonitrile (800mL) was stirred at 60 ℃ for 1 hour (h). After the solid began to precipitate, the mixture was left at room temperature for 4 h. The solid was collected, washed with minimal acetonitrile and dried to give the salts of (L) -leucinamide and trans- (1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxylate as white solids: (38.9g, 95% ee, 43%):1H NMR(400MHz,DMSO-d6)7.80(s,1H),7.73(m,2H),7.49(dd,J＝10.7,8.6Hz,1H),7.31(s,1H),3.53(dd,J＝7.9,6.4Hz,1H),3.34(d,J＝8.6Hz,1H),3.07(d,J＝8.6Hz,1H),1.77-1.60(m,1H),1.60-1.40(m,2H),0.89(t,J＝6.7Hz,6H)；19F NMR(376MHz,DMSO-d6)-59.88,-117.93。
the white solid salt was diluted with EtOAc and washed with 1.5 standard (N) HCl and water. Subjecting the organic layer to Na2SO4Dried, filtered and concentrated to give the title product as a white solid (27.3g, 95% ee, 43% yield):1H NMR(400MHz,DMSO-d6)13.24(s,1H),8.03-7.71(m,2H),7.54(dd,J＝10.6,8.7Hz,1H),3.65-3.51(m,2H)；19F NMR(376MHz,DMSO-d6)-59.93,-117.06；ESIMS m/z＝316([M-H]-)。
example 9: preparation of tert-butyl-N- ((tert-butoxy) carbonyl) -N- (3- (5-amino-2-chlorobenzoylamino) -2, 6-difluorophenyl) carbamate (C11)
The title compound was prepared from tert-butyl-N- ((tert-butoxy) carbonyl) -N- (3- (2-chloro-5-nitrobenzamido) -2, 4-difluorophenyl) carbamate (C12) according to the method disclosed in heimstra, r.j. et al, us patent 9,781,935B2(WO 2016/168059) as example 83 and isolated as a white solid (2.89g, 59%):1H NMR(400MHz,DMSO-d6)10.28(s,1H),7.67(td,J＝8.8,5.8Hz,1H),7.24(td,J＝9.3,1.7Hz,1H),7.13(d,J＝8.6Hz,1H),6.73(d,J＝2.7Hz,1H),6.65(dd,J＝8.6,2.8Hz,1H),5.48(s,2H),1.40(s,18H)；19F NMR(376MHz,DMSO-d6)-123.86,-126.24；ESIMS m/z 496([M-H]-)。
example 10: preparation of tert-butyl-N- ((tert-butoxy) carbonyl) -N- (3- (2-chloro-5-nitrobenzamido) -2, 4-difluorophenyl) carbamate (C12)
From 2-chloro-5-nitrobenzoic acid and tert-butyl according to the method disclosed in Heemstra, R.J. et al, U.S. Pat. No. 9,781,935B2(WO 2016/168059) in example 28The title compound was prepared from yl-N- ((tert-butoxy) carbonyl) -N- (3-amino-2, 6-difluorophenyl) carbamate (C13) and isolated as a yellow oil (5.2g, 66%):1H NMR(400MHz,DMSO-d6)10.69(s,1H),8.51(d,J＝2.7Hz,1H),8.35(dd,J＝8.8,2.8Hz,1H),7.97-7.79(m,2H),7.30(td,J＝9.3,1.7Hz,1H),1.41(s,18H)；19F NMR(376MHz,DMSO-d6)-123.43,-127.02(d,J＝2.0Hz)；ESIMS m/z 526([M-H]-)。
example 11: preparation of tert-butyl-N- ((tert-butoxy) carbonyl) -N- (3-amino-2, 6-difluorophenyl) carbamate (C13)
The title compound was prepared from tert-butyl-N- ((tert-butoxy) carbonyl) -N- (2, 6-difluoro-3-nitrophenyl) carbamate (C14) according to the method disclosed in example 91 of heimstra, r.j. et al, us patent 9,781,935B2(WO 2016/168059), and isolated as a white solid (5.06g, 100%):1H NMR(400MHz,DMSO-d6)6.87(td,J＝9.3,1.7Hz,1H),6.74(td,J＝9.4,5.7Hz,1H),5.12(s,2H),1.39(s,18H)；19FNMR(376MHz,DMSO-d6)-137.96(d,J＝3.7Hz),-141.10(d,J＝3.7Hz)；ESIMS m/z 244([M-BOC]-)。
example 12: preparation of tert-butyl-N- ((tert-butoxy) carbonyl) -N- (2, 6-difluoro-3-nitrophenyl) carbamate (C14)
The title compound was prepared from 2, 6-difluoro-5-nitroaniline according to the method disclosed in Heemstra, r.j. et al, us patent 9,781,935B2(WO 2016/168059) in example 89 and isolated as a white foam (5.2g, 69%):1H NMR(300MHz,CDCl3)8.14(ddd,J＝9.2,8.1,5.5Hz,1H),7.10(ddd,J＝9.7,8.0,2.0Hz,1H),1.45(s,18H)；19F NMR(376MHz,CDCl3)-105.95(dd,J＝10.9,2.7Hz),-119.53(d,J＝10.6Hz)；ESIMS m/z 397([M+Na]+)。
example 13: preparation of tert-butyl-N- ((tert-butoxy) carbonyl) -N- (3- (2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxamido) benzamido) -2, 6-difluorophenyl) carbamate (DP1)
The title compound was prepared according to the method disclosed in Heemstra, r.j. et al, us patent 9,781,935B2(WO 2016/168059) in example 13 from (1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxylic acid (C8) and tert-butyl-N- ((tert-butoxy) carbonyl) -N- (3- (5-amino-2-chlorobenzamido) -2, 6-difluorophenyl) carbamate (C11) and isolated as a white solid (0.171g, 64%).
Example 14: preparation of N- (3-amino-2, 4-difluorophenyl) -2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxamido) benzamide (DP2)
The title compound was prepared according to the method disclosed in Heemstra, r.j. et al, us patent 9,781,935B2(WO 2016/168059) as example 62 from tert-butyl-N- ((tert-butoxy) carbonyl) -N- (3- (2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxamide) benzamido) -2, 6-difluorophenyl) carbamate (DP1) and isolated as a white solid (0.108g, 84%).
The following compounds were prepared in a similar manner to the procedures outlined in the examples above or by the methods disclosed in the schemes (see above):
n- (3-amino-2, 4-difluorophenyl) -2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3, 4-dichlorophenyl) cyclopropane-1-carboxamido) benzamide (DP3)
Isolated as a white solid (0.115g, 89%).
N- (3-amino-2, 4-difluorophenyl) -2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-chloro-4-fluorophenyl) cyclopropane-1-carboxamido) benzamide (DP4)
Isolated as a white solid (0.087g, 84%).
N- (3-amino-2, 4-difluorophenyl) -2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) benzamide (DP5)
Isolated as a white foam (0.043g, 53%).
N- (3-amino-2, 4-difluorophenyl) -2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) benzamide (DP6)
Isolated as a white solid (0.860g, 85%).
trans-N- (3-amino-2, 4-difluorophenyl) -5- (3- (3, 5-bis (trifluoromethyl) phenyl) -2, 2-dichlorocyclopropane-1-carboxamido) -2-chlorobenzamide (DP7)
Isolated as a white foam (1.27g, 98%).
N- (3-amino-2, 4-difluorophenyl) -2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-fluoro-5- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) benzamide (DP8)
Isolated as a white solid (0.784g, 87%).
Example 15: preparation of 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) thio) acetamido) phenyl) benzamide (F15)
To a magnetically stirred solution of N- (3-amino-2, 4-difluorophenyl) -2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) benzamide (DP 5; 250 mg, 0.419 mmol)) in ethyl acetate (4 mL (mL)) was added 2- ((2,2, 2-trifluoroethyl) thio) acetic acid (77mg, 0.440mmol), followed by pyridine (134 microliters (μ L), 1.26mmol) and 2,4, 6-tripropyl-1, 3,5,2,4, 6-trioxatriphospha-cyclohexane 2,4, 6-trioxide (R: (R), N- (3-amino-2, 4-difluorophenyl) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) benzamide (DP 5; 250 mg, 0.419 mmol))
The following compounds were prepared in analogy to the procedure outlined in example 15: 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (3- (2, 2-difluoro-2- (methylthio) acetamido) -2, 4-difluorophenyl) benzamide (F1)
Isolated as a white solid (29mg, 46%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- (pyridin-4-ylthio) acetamido) phenyl) benzamide (F2)
Isolated as a light brown foam (82mg, 79%).
N- (3- (2- (allylthio) acetamido) -2, 4-difluorophenyl) -2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) benzamide (F3)
Isolated as a white solid (85mg, 85%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((4-fluorophenyl) thio) acetamido) phenyl) benzamide (F4)
Isolated as a white solid (80mg, 74%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((3,3, 3-trifluoropropyl) thio) acetamido) phenyl) benzamide (F5)
Isolated as a white solid (81mg, 80%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) thio) acetamido) phenyl) benzamide (F6)
Isolated as a white solid (122mg, 75%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) propionamido) phenyl) benzamide (F7)
Isolated as a white solid (129mg, 80%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) acetamido) phenyl) benzamide (F8)
Isolated as a white solid (125mg, 79%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3, 4-dichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) thio) acetamido) phenyl) benzamide (F9)
Isolated as a white solid (136mg, 68%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3, 4-dichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) propionamido) phenyl) benzamide (F10)
Isolated as a white solid (142mg, 73%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3, 4-dichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) acetamido) phenyl) benzamide (F11)
Isolated as a white solid (152mg, 79%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-chloro-4-fluorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) thio) acetamido) phenyl) benzamide (F12)
Isolated as a white solid (141mg, 70%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-chloro-4-fluorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) propionamido) phenyl) benzamide (F13)
Isolated as a white solid (151mg, 76%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-chloro-4-fluorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) acetamido) phenyl) benzamide (F14)
Isolated as a white solid (143mg, 74%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) propionamido) phenyl) benzamide (F16)
Isolated as a white solid (302mg, 91%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) acetamido) phenyl) benzamide (F17)
Isolated as a white solid (426mg, 83%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (3- (2- (ethylthio) propionamido) -2, 4-difluorophenyl) benzamide (F18)
Isolated as a white foam (101mg, 80%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (3- (2- (ethylthio) acetamido) -2, 4-difluorophenyl) benzamide (F19)
Isolated as a white solid (117mg, 95%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (3- (phenylthio) propionamido) phenyl) benzamide (F20)
Isolated as a white solid (89mg, 83%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (3- ((3,3, 3-trifluoropropyl) thio) propionamido) phenyl) benzamide (F21)
Isolated as a white solid (77mg, 74%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (3- ((trifluoromethyl) thio) propionamido) phenyl) benzamide (F22)
Isolated as a white solid (83mg, 83%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (3- (3- (ethylthio) propionamido) -2, 4-difluorophenyl) benzamide (F23)
Isolated as a white solid (61mg, 65%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (3- (methylthio) propionamido) phenyl) benzamide (F24)
Isolated as a white solid (72mg, 78%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (4- (methylthio) butanamido) phenyl) benzamide (F25)
Isolated as a white solid (57mg, 60%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (3- ((trifluoromethyl) sulfonyl) propionamido) phenyl) benzamide (F46)
Isolated as a white solid (55mg, 53%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) acetamido) phenyl) benzamide (F47)
Isolated as a white solid (74mg, 75%).
Trans-5- (3- (3, 5-bis (trifluoromethyl) phenyl) -2, 2-dichlorocyclopropane-1-carboxamido) -2-chloro-N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) acetamido) phenyl) benzamide (F48)
Isolated as a white foam (110mg, 90%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-fluoro-5- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) acetamido) phenyl) benzamide (F49)
Isolated as a white solid (70mg, 84%).
Example 16: preparation of 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3, 4-dichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) sulfinyl) acetamido) phenyl) benzamide (F30) and 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3, 4-dichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) sulfonyl) acetamido) phenyl) benzamide (F42).
To 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3, 4-dichlorophenyl) cyclopropane-1-carboxamide) -N- (2, 4-difluoro) at 0 deg.C-3- (2- ((2,2, 2-trifluoroethyl) thio) acetamido) phenyl) benzamide (F9; 78mg, 0.11mmol) in 1, 2-dichloroethane (DCE; 2.1mL) was added 3-chloroperoxybenzoic acid (34.1mg, 0.148mmol) and the resulting colorless solution was allowed to slowly warm to room temperature over a 16 hour period. Analysis of the milky reaction mixture (white precipitate) by LCMS indicated complete consumption of the starting material, conversion to sulfoxide (92%) and sulfone (8%). The mixture was warmed to 45 ℃ and stirred overnight to give the sulfoxide and sulfone products in a 43:56 ratio. The milky reaction mixture was diluted with ethyl acetate (15mL) and the resulting solution was washed successively with 10% aqueous sodium bisulfite (2X 5mL), saturated aqueous sodium bicarbonate (5mL), and saturated aqueous sodium chloride (brine; 5mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by automatic flash chromatography (SiO)2(ii) a 0% -90% ethyl acetate in hexanes) to give the title compound as a white solid (F30, 30mg, 38%; f42, 41mg, 51%).
The following compounds were prepared in analogy to the procedure outlined in example 16: 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) sulfinyl) acetamido) phenyl) benzamide (F26)
Isolated as a white solid (22mg, 32%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) sulfinyl) acetamido) phenyl) benzamide (F29)
Isolated as a white solid (27mg, 40%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) sulfonyl) propionamido) phenyl) benzamide (F35)
Isolated as a white solid (27mg, 35%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) sulfonyl) acetamido) phenyl) benzamide (F36)
Isolated as a white solid (32mg, 46%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3, 4-dichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) sulfonyl) propionamido) phenyl) benzamide (F37)
Isolated as a white solid (30mg, 32%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3, 4-dichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) sulfonyl) acetamido) phenyl) benzamide (F38)
Isolated as a white solid (70mg, 69%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3,4, 5-trichlorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) sulfonyl) acetamido) phenyl) benzamide (F41)
Isolated as a white solid (32mg, 47%).
Example 17: preparation of 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) sulfinyl) acetamido) phenyl) benzamide (F33)
To a solution of 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) thio) acetamido) phenyl) benzamide (F17; 197mg, 0.267mmol) in acetic acid (2.7mL) was added sodium perborate tetrahydrate (62mg, 0.40mmol) and the resulting milky mixture was warmed to 55 ℃ and stirred for 16 h. The reaction mixture was warmed to 65 ℃ and stirred for 5 hours, cooled to 55 ℃ and treated with additional perborate (12mg, 0.053 mmol). The milky reaction mixture was stirred at 55 ℃ for 16 h, cooled to room temperature, diluted with dichloromethane (50mL) and carefully neutralized with saturated aqueous sodium bicarbonate. The phases were separated and the aqueous phase was extracted with additional dichloromethane (10 mL). The combined organic phases were washed with brine (25mL) and dried by passage through a phase separation column. The solvent was evaporated and the resulting residue was purified by automatic flash chromatography (SiO)2(ii) a 0% -60% ethyl acetate in hexanes) to give the title compound as a white solid (19mg, 9.4%).
The following compounds were prepared in analogy to the procedure outlined in example 17:
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) sulfinyl) acetamido) phenyl) benzamide (F32)
Isolated as a white solid (118mg, 62%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) sulfonyl) acetamido) phenyl) benzamide (F44)
Isolated as a white solid (47mg, 24%).
Example 18: preparation of 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (3- (2- (ethylsulfinyl) propionamido) -2, 4-difluorophenyl) benzamide (F34)
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (3- (2- (ethylthio) propionamido) -2, 4-difluorophenyl) benzamide (F18) (0.130g, 0.182mmol) was dissolved in hexafluoroisopropanol (5 mL). 30% aqueous hydrogen peroxide (0.083g, 0.729mmol) was added at room temperature. After 2 hours, the reaction mixture was poured into ethyl acetate (50mL) and washed with saturated aqueous sodium bisulfite (10mL) and water (10 mL). The organic extracts were concentrated under vacuum on a rotary evaporator and the resulting crude product was purified by silica and C-18 flash chromatography to give the title compound (0.066g, 47%) as a white foam (mixture of diastereomers).
Example 19: preparation of 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (3- (2- (ethylsulfonyl) propanamido) -2, 4-difluorophenyl) benzamide (F45)
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (3- (2- (ethylthio) propionamido) -2, 4-difluorophenyl) benzamide (F18) (0.093g, 0.130mmol) was dissolved in 2mL of methanol (2 mL). Adding at room temperature(0.100g, 0.326 mmol). After 20 h, the reaction mixture was poured into ethyl acetate (50mL) and washed with saturated aqueous sodium bisulfite (10mL) and water (10 mL). The organic extracts were concentrated under vacuum on a rotary evaporator and the resulting crude product was purified by flash chromatography on silica gel to give the title compound as a white solid (0.079g, 77%).
The following compounds were prepared in analogy to the procedure outlined in example 19: 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-chloro-4-fluorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) sulfinyl) propionamido) phenyl) benzamide (F27)
Isolated as a white solid (28mg, 24%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-chloro-4-fluorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) sulfinyl) acetamido) phenyl) benzamide (F28)
Isolated as a light brown solid (13mg, 15%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-chloro-4-fluorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) sulfinyl) acetamido) phenyl) benzamide (F31)
Isolated as a white solid (16mg, 19%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-chloro-4-fluorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) sulfonyl) propionamido) phenyl) benzamide (F39)
Isolated as a white solid (27mg, 25%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-chloro-4-fluorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((trifluoromethyl) sulfonyl) acetamido) phenyl) benzamide (F40)
Isolated as a light brown solid (30mg, 32%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (3-chloro-4-fluorophenyl) cyclopropane-1-carboxamido) -N- (2, 4-difluoro-3- (2- ((2,2, 2-trifluoroethyl) sulfonyl) acetamido) phenyl) benzamide (F43)
Isolated as a white solid (54mg, 63%).
The following compounds were prepared in analogy to the procedure outlined in example 15:
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2-fluoro-4- (2- (methylthio) acetamido) phenyl) benzamide (F50)
Isolated as a white solid (38mg, 50%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2-fluoro-4- (2- ((trifluoromethyl) thio) acetamido) phenyl) benzamide (F51)
Isolated as a pale yellow foam (58mg, 75%).
2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) -N- (2-fluoro-4- (2- ((2,2, 2-trifluoroethyl) thio) acetamido) phenyl) benzamide (F52)
Isolated as a white foam (59mg, 75%).
Example 20: preparation of tert-butyl N- (4-amino-3-fluorophenyl) -N-tert-butoxycarbonyl-carbamate (C15)
The title compound was prepared from tert-butyl N-tert-butoxycarbonyl-N- (3-fluoro-4-nitro-phenyl) carbamate according to the procedure disclosed in example 91 of haemstra, r.j. et al, us patent 9,781,935B2, and was isolated as a peach-colored solid (3.475g, 100%): mp 77-82 ℃;1H NMR(300MHz,DMSO-d6)6.90-6.83(m,1H),6.74-6.64(m,2H),5.23(s,2H),1.38(s,18H)；19F NMR(564MHz,DMSO-d6) -134.64, -134.66, -134.66, -134.68; for C16H23FN2O4Calculated HRMS-ESI (M/z) [ M +]+326.1642; the found value is: 326.1646.
example 21: preparation of 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) benzoic acid (C16)
The title compound was prepared according to the method disclosed in Heemstra, r.j, et al, U.S. patent application publication No. 2018/0098541a1, example 39, from (1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxylic acid (C10, as prepared in Heemstra, r.j, et al, U.S. patent application publication No. 2018/0098541a 1) and 5-amino-2-chlorobenzoic acid and isolated as a brown solid (5.80g, 93%):1H NMR(400MHz,DMSO-d6)13.48(s,1H),10.94(s,1H),8.17(d,J＝2.7Hz,1H),7.94-7.72(m,3H),7.68-7.44(m,2H),3.68(d,J＝8.4Hz,1H),3.49(d,J＝8.5Hz,1H)；19F NMR(376MHz,DMSO-d6)-59.93(d,J＝12.6Hz),-116.95(q,J＝12.5Hz)；ESIMS m/z 472([M+H]+)。
example 22: preparation of tert-butyl N-tert-butoxycarbonyl-N- [4- [ [ 2-chloro-5- [ [ (1R,3R) -2, 2-dichloro-3- [ 4-fluoro-3- (trifluoromethyl) phenyl ] cyclopropane-carbonyl ] amino ] benzoyl ] amino ] -3-fluoro-phenyl ] carbamate (C17)
The title compound was prepared from tert-butyl N- (4-amino-3-fluorophenyl) -N-tert-butoxycarbonyl-carbamate (prepared from tert-butyl N-tert-butoxycarbonyl-N- (3-fluoro-4-nitro-phenyl) carbamate according to the method disclosed in haemstra, r.j. et al, example 91 in us 9,781,935B2, example 15 for F602) and 2-chloro-5- ((1R,3R) -2, 2-dichloro-3- (4-fluoro-3- (trifluoromethyl) phenyl) cyclopropane-1-carboxamido) benzoic acid (C16) according to the method disclosed in haemstra, r.j. et al, us 9,781,935B2, and isolated as a white solid (0.606g, 89 percent of: mp 128-132 deg.C;1H NMR(300MHz,DMSO-d6)10.98(s,1H),10.49(s,1H),7.94-7.75(m,5H),7.63-7.54(m,2H),7.31(dd,J＝11.3,2.4Hz,1H),7.09(d,J＝8.6Hz,1H),3.70(d,J＝8.5Hz,1H),3.52(d,J＝8.5Hz,1H),1.41(s,18H)；19F NMR(471MHz,DMSO-d6) -59.91(d, J ═ 12.3Hz), -116.93(ddq, J ═ 18.3,12.2,6.4Hz), -121.42-121.52 (m); for C34H31Cl3F5N3O6Calculated HRMS-ESI (M/z) [ M +]+777.1199; the found value is: 777.1192.
example 23: preparation of N- (4-amino-2-fluoro-phenyl) -2-chloro-5- [ [ (1R,3R) -2, 2-dichloro-3- [ 4-fluoro-3- (trifluoromethyl) phenyl ] cyclopropanecarbonyl ] -amino ] benzamide (C18)
The procedure disclosed for F175 in example 62 of Heemstra, R.J. et al, U.S. Pat. No. 9,781,935B2, was followed from tert-butyl N-tert-butoxycarbonyl-N- [4- [ [ 2-chloro-5- [ [ (1R,3R) -2, 2-dichloro-3- [ 4-fluoro-3- (trifluoromethyl) phenyl ] amino acid]Cyclopropane-carbonyl]Amino group]Benzoyl radical]Amino group]-3-fluoro-phenyl]Carbamate (C17) to prepare the title compound and isolate as a brown foam (0.502g, 94%):1H NMR(500MHz,DMSO-d6)10.92(s,1H),9.82(s,1H),7.89-7.80(m,3H),7.74(dd,J＝8.8,2.6Hz,1H),7.59(dd,J＝10.7,8.7Hz,1H),7.52(d,J＝8.8Hz,1H),7.17(t,J＝8.6Hz,1H),6.45-6.35(m,2H),5.37(s,2H),3.69(d,J＝8.5Hz,1H),3.50(d,J＝8.5Hz,1H)；19F NMR(471MHz,DMSO-d6) -59.91(d, J ═ 12.3Hz), -116.94(ddq, J ═ 18.3,12.3,6.5Hz), -122.15(dd, J ═ 12.3,8.8 Hz); for C24H15Cl3F5N3O2Calculated HRMS-ESI (M/z) [ M +]+577.0150; the found value is: 577.0152.
it will be recognized that certain reagents and reaction conditions may not be compatible with certain formula one molecules or certain functions that may be present in certain molecules used in the preparation of certain formula one molecules. In such cases, it may be necessary to employ standard protection and deprotection protocols which are well reported in the literature and well known to those skilled in the art. In addition, in certain cases, it may be necessary to perform other conventional synthetic steps not described herein to complete the synthesis of the desired molecule. One skilled in the art will also recognize that synthesis of the desired molecule may be achieved by performing some of the steps of the synthetic route in a different order than that described. One skilled in the art will also recognize that standard functional group interchange or substitution reactions can be performed on the desired molecule to introduce or modify substituents.
Biological assay
The following bioassays for Beet Armyworm (Beet Armyworm, Spodoptera exigua), Trichoplusia ni (CabbageLooper, Trichoplusia ni), and Yellow Fever Mosquito (Aedes aegypti) are included herein for the damage suffered by them. In addition, beet armyworm and cabbage looper are two good indicator species of a wide range of chewing pests. Furthermore, myzus persicae (green peach aphid) is a good indicator of pests feeding sap on a large scale. The results using these indicator species and yellow fever mosquitoes show the broad utility of the molecule of formula one in controlling pests of the arthropoda, mollusca, and nematode phyla (Drewes et al)
Example a: bioassay for beet armyworm (Spodoptera exigua, LAPHEG) ("BAW") and Trichoplusia ni ("CL")
Beet armyworm is a serious pest that presents economic problems for alfalfa, asparagus, beets, citrus, corn, cotton, onions, peas, peppers, potatoes, soybeans, sugar beet, sunflowers, tobacco, and tomatoes, among other crops. Beet armyworm is native to southeast asia, but is now found in africa, australia, japan, north america, and south europe. Larvae can feed in large flocks, resulting in destructive crop losses. It is known to be resistant to several pesticides.
Cabbage loopers are serious pests found throughout the world. It affects alfalfa, beans, beets, broccoli, kohlrabi (Brussel sprouts), cabbage, cantaloupe, cauliflower, celery, savoy cabbage, cotton, cucumber, eggplant, kale, lettuce, melons, mustard, parsley, pea, pepper, potato, soybean, spinach, squash, tomato, turnip, and watermelon, among other crops. This species is very destructive to the plant due to its greedy appetite. Larvae eat three times their weight of food per day. The feeding site is marked by a large accumulation of viscous wet fecal material that can cause high disease stress, causing secondary problems to the plant at the site. It is known to be resistant to several pesticides.
Therefore, due to the above factors, it is important to control these harmful organisms. In addition, molecules that control these pests known as chew pests (BAW and CL) would be useful for controlling other pests that chew plants.
Certain molecules disclosed in this document were tested against BAW and CL using the procedures described in the examples below. In reporting the results, a "BAW & CL rating table" (see table section) was used.
Bioassay of BAW
Bioassays for BAW were performed using a 128-well diet tray assay. One to five second-instar BAW larvae were placed in each well (3mL) of a diet tray previously filled with about 1mL artificial diet, which had been applied (each of eight wells) 50 μ g/cm2The molecules were tested (dissolved in 50 μ L of a 90:10 acetone-water mixture) and then allowed to dry. The trays were covered with a clear self-adhesive cover, vented to allow gas exchange, and kept at 25 ℃ in 14:10 light-dark for five to seven days. Recording the percent mortality of larvae from each well; the activity of the eight wells was then averaged. The results are shown in table titled "table ABC: biological results "(see table section).
Bioassay of CL
Bioassay of CL was performed using a 128-well diet tray assay. One to five second instar CL larvae were placed in each well (3mL) of a diet tray previously filled with about 1mL artificial diet, which had been applied (each of eight wells) 50 μ g/cm2The molecules were tested (dissolved in 50 μ L90:10 acetone-water mixture) and then allowed to dry. The trays were covered with a clear self-adhesive cover, vented to allow gas exchange, and kept at 25 ℃ in 14:10 light-dark for five to seven days. Recording the percent mortality of larvae from each well; the activity of the eight wells was then averaged. The results are shown in table titled "table ABC: biological results "(see table section).
Example B: bioassay for Myzus persicae (MYZUPE) ("GPA").
GPA is the most important aphid pest of peach trees and causes growth decline, leaf blight, and death of various tissues. Myzus persicae is also dangerous because it acts as a vehicle for the transmission of plant viruses (such as potato virus Y and potato leafroll virus) to members of the solanaceae solanum/potato family and for the transmission of various mosaic viruses to many other food crops. GPA attacks, inter alia, plants such as: broccoli, burdock, cabbage, carrot, cauliflower, white radish, eggplant, green bean, lettuce, macadamia, papaya, capsicum, sweet potato, tomato, watercress, and pumpkin, among other crops. GPA also attacks many ornamental crops such as carnation, chrysanthemum, flowering white cabbage, poinsettia, and roses. GPA has developed resistance to many pesticides. At present, it is the third most reported number of insect-resistant cases of pests (Sparks et al). Therefore, due to the above factors, it is important to control such harmful organisms. In addition, molecules that control such pests known as sap-feeding pests (GPA) may be used to control other pests that feed on sap-sucking from plants.
Certain molecules disclosed in this document were tested against GPA using the procedure described in the examples below. In reporting the results, a "GPA & YFM rating Table" (see Table section) was used.
Cabbage seedlings with 2-3 small (3-5cm) true leaves grown in 3-inch pots were used as the test substrate. One day before chemical application, seedlings were infected with 20-50 GPA (wingless adult and nymph stage). Four pots with individual seedlings were used for each treatment. Test molecules (2mg) were dissolved in 2mL of acetone/methanol (1:1) solvent to form a 1000ppm stock solution of test molecules. This stock solution was diluted 5-fold with 0.025% Tween 20 in water to give a solution of 200ppm test molecule. Using a hand-held suction sprayer, the solution was sprayed onto both sides of the cabbage leaves until run off occurred. The reference plants were sprayed with a dilution containing only 20% by volume of acetone/methanol (1:1) solvent (solvent check). Prior to grading, the treated plants were stored in a holding room at about 25 ℃ and ambient Relative Humidity (RH) for 3 days. Evaluation was carried out by counting the number of live aphids per plant under a microscope. The percent control was measured using the Abbott's correction formula (W.S. Abbott, "A Method of calculating the efficacy of an Insecticide", J.Econ.entomol. [ journal of economics ]18(1925), pp. 265-. Corrected% control is 100X (X-Y)/X, where X is the number of live aphids on the solvent control plant and Y is the number of live aphids on the treated plant. The results are shown in table titled "table ABC: biological results "(see table section).
Example C: bioassay of yellow fever mosquito (Aedes aegypti, AEDSAE) ("YFM").
YFM is more inclined to feed on humans during the daytime and is most often found in or near human dwellings. YFM is a vector that transmits several diseases. It is a mosquito that can disseminate dengue and yellow fever viruses. Yellow fever is the second most dangerous mosquito-borne disease after malaria. Yellow fever is an acute viral hemorrhagic disease and up to 50% of severely ill people will die of yellow fever without treatment. It is estimated that there are 200,000 yellow fever cases worldwide each year, resulting in 30,000 deaths. Dengue is an inland viral disease; it is sometimes referred to as "broken bone heat" (or "broken-heart heat") because of the intense pain it can cause. Dengue kills about 20,000 people each year. Therefore, due to the above factors, it is important to control such harmful organisms. In addition, molecules that control this pest, known as the sucking pest (YFM), can be used to control other pests that cause illness in humans and animals.
Certain molecules disclosed in this document were tested against YFM using the procedure described in the following paragraphs. In reporting the results, a "GPA & YFM rating Table" (see Table section) was used.
A master containing 400. mu.g of molecules (equivalent to a 4000ppm solution) dissolved in 100. mu.L of dimethyl sulfoxide (DMSO) was used. The master contained 15 μ L of assembly molecules per well. To each well of this plate was added 135. mu.L of a 90:10 water/acetone mixture. A robot (a)
On the day before the plates were to be treated, mosquito eggs were placed in Millipore (Millipore) water containing liver powder to begin hatching (4g in 400 mL). After the "daughter" plate was formed using a robot, it was infested with 220 μ L of liver powder/mosquito larvae (about 1 day old larvae) mixture. After the plates were infested with mosquito larvae, the plates were covered with a non-evaporative cover to reduce drying. The plates were kept at room temperature for 3 days before fractionation. After 3 days, wells were observed and scored based on mortality. The results are shown in table titled "table ABC: biological results "(see table section).
Agriculturally acceptable acid addition salts, salt derivatives, solvates, ester derivatives, polymorphs, isotopologues and radionuclides
The molecule of formula one may be formulated as an agriculturally acceptable acid addition salt. As non-limiting examples, the amine functional group may form a salt with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, acetic acid, benzoic acid, citric acid, malonic acid, salicylic acid, malic acid, fumaric acid, oxalic acid, succinic acid, tartaric acid, lactic acid, gluconic acid, ascorbic acid, maleic acid, aspartic acid, benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, hydroxymethanesulfonic acid, and hydroxyethanesulfonic acid. Additionally, as a non-limiting example, the acid functionality may form a salt, including salts derived from alkali or alkaline earth metals and salts derived from ammonia and amines. Examples of preferred cations include sodium, potassium, and magnesium.
The molecule of formula one may be formulated as a salt derivative. By way of non-limiting example, salt derivatives may be prepared by contacting the free base with the desired acid in an amount sufficient to produce a salt. The free base can be regenerated by treating the salt with a suitable dilute aqueous base solution, such as dilute aqueous sodium hydroxide, potassium carbonate, ammonia, and sodium bicarbonate. For example, in many cases, pesticides (e.g., 2,4-D) are more soluble in water by converting them to their dimethylamine salts.
The molecule having formula one can be formulated with a solvent into a stable complex such that the complex remains intact after removal of the non-complexing solvent. These complexes are often referred to as "solvates". However, it is particularly desirable to use water as a solvent to form stable hydrates.
The molecule of formula one containing an acid functional group can be made into an ester derivative. These ester derivatives can then be applied in the same manner as the molecules disclosed in this document are applied.
The molecule of formula one can be made into multiple polymorphs. Polymorphism is important in agrochemical development because different crystal polymorphs or structures of the same molecule can have vastly different physical and biological properties.
Molecules having formula one can be made with different isotopes. Of particular importance is to have2H (also known as deuterium) or3H (also known as tritium) substitution1A molecule of H. Molecules of formula one can be made with different radionuclides. Of particular importance is to have14C (also known as radioactive carbon). With deuterium, tritium, or14The molecule of formula one of C is useful for biological studies, and half-life studies, as well as MoA studies that allow for tracking in chemical and physiological processes.
Combination of
In another embodiment of the invention, the molecule of formula one may be used in combination with one or more active ingredients (such as in the form of a mixture of components, or applied simultaneously or sequentially).
In another embodiment of the present disclosure, the molecule of formula one may be used in combination (e.g., in the form of a mixture of components, or applied simultaneously or sequentially) with one or more active ingredients each having a MoA that is the same as, similar to, but more likely-different from the MoA of the molecule of formula one.
In another embodiment, the molecule of formula one may be used in combination (such as in a mixture of components, or applied simultaneously or sequentially) with one or more molecules having acaricidal, algicidal, avicidal, bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal, nematicidal, rodenticidal, and/or virucidal properties.
In another embodiment, the molecule of formula one may be used in combination (such as in a mixture of components, or applied simultaneously or sequentially) with one or more molecules that are antifeedants, bird repellents, chemosterilants, herbicide safeners, insect attractants, insect repellents, mammal repellents, mating disrupters, plant activators, plant growth regulators, and/or synergists.
In another embodiment, the molecule of formula one may also be used in combination with one or more biotype of pesticide (such as in a mixture of components, or applied simultaneously or sequentially).
In another embodiment, the combination of the molecule of formula one and the active ingredient in the pesticidal composition may be used in a wide variety of weight ratios. For example, in a two-component mixture, the weight ratio of the molecule of formula one to the active ingredient may be used in the weight ratios in table B. In general, however, weight ratios of less than about 10:1 to about 1:10 are preferred. It is also sometimes preferred to use mixtures of three, four, five, six, seven or more components comprising the molecule of formula one and additionally two or more active ingredients.
The weight ratio of the molecule of formula one to the active ingredient can also be depicted as X: Y; wherein X is the weight part of the molecule of formula one and Y is the weight part of the active ingredient. The numerical range of parts by weight of X is 0< X.ltoreq.100 and the numerical range of parts by weight of Y is 0< Y.ltoreq.100, and is graphically shown in Table C. As a non-limiting example, the weight ratio of the molecule of formula one to the active ingredient may be 20: 1.
The weight ratio range of the molecule of formula one to the active ingredient can be depicted as X1:Y1To X2:Y2Wherein X and Y are as defined above.
In one embodiment, the weight ratio may range from X1:Y1To X2:Y2Wherein X is1>Y1And X2<Y2. As a non-limiting example, the weight ratio of the molecule of formula one to the active ingredient can be 3:1 to 1:3, inclusive.
In another embodiment, the weight ratio may range from X1:Y1To X2:Y2Wherein X is1>Y1And X2>Y2. As a non-limiting example, the weight ratio of molecules of formula one to active ingredient can be from 15:1 to 3:1, inclusive.
In another embodiment, the weight ratio may range from X1:Y1To X2:Y2Wherein X is1<Y1And X2<Y2. By way of non-limiting example, the weight ratio of the molecule of formula one to the active ingredient can be from about 1:3 to about 1:20, inclusive.
Formulations
Pesticides are many times not suitable for use in their pure form. It is often necessary to add additional materials so that the pesticide can be used at the desired concentration and in the appropriate form, allowing for ease of application, handling, transportation, storage, and maximum pesticide activity. Thus, pesticides are formulated into, for example, baits, concentrated emulsions, powders, emulsifiable concentrates, fumigants, gels, granules, microcapsules, seed treatments, suspension concentrates, suspoemulsions, tablets, water-soluble liquids, water-dispersible granules or dry flowable agents, wettable powders, and ultra-low volume solutions.
Pesticides are most often applied in the form of aqueous suspensions or emulsions prepared from concentrated formulations of such pesticides. Such water-soluble, water-suspendable or emulsifiable formulations are liquids which are usually referred to as solids (wettable powders, water-dispersible granules), usually as emulsifiable concentrates or aqueous suspensions. Wettable powders which can be compacted to form water dispersible granules contain an intimate mixture of the pesticide, the carrier and the surfactant. The concentration of the pesticide is typically from about 10% to about 90% by weight. The support is typically selected from attapulgite (attapulgite) clay, montmorillonite (montmorillonite) clay, diatomaceous earth, or purified silicate. Effective surfactants, which comprise from about 0.5% to about 10% of the wettable powder, are found in the group of sulfonated lignins, condensed naphthalene sulfonates, alkylbenzene sulfonates, alkyl sulfates, and nonionic surfactants such as ethylene oxide adducts of alkylphenols.
Emulsifiable concentrates of the pesticide include a suitable concentration of the pesticide (e.g., about 50 to about 500 grams per liter of liquid) dissolved in a carrier which is a water-miscible solvent or a mixture of a water-immiscible organic solvent and an emulsifier. Useful organic solvents include aromatics (especially xylenes) and petroleum fractions (especially the high boiling naphthalene and olefin portions of petroleum, such as heavy aromatic naphtha). Other organic solvents may also be used, such as terpene solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and miscellaneous alcohols such as 2-ethoxyethanol. Suitable emulsifiers for the emulsifiable concentrates are selected from the group consisting of conventional anionic surfactants and nonionic surfactants.
Aqueous suspensions include suspensions of water-insoluble pesticides dispersed in an aqueous carrier at a concentration of about 5% to about 50% by weight. The suspension was prepared by: the pesticide is finely ground and vigorously mixed into a carrier consisting of water and surfactant. Ingredients such as inorganic salts and synthetic or natural gums may also be added to increase the density and viscosity of the aqueous carrier. It is generally most effective to simultaneously grind and mix the pesticide by preparing and homogenizing an aqueous mixture in an apparatus such as a sand mill, ball mill, or piston-type homogenizer. The pesticide in suspension may be microencapsulated in a plastic polymer.
Oil Dispersions (ODs) include suspensions of an organic solvent-insoluble pesticide finely dispersed in a mixture of an organic solvent and an emulsifier at a concentration of about 2% to about 50% by weight. One or more pesticides may be dissolved in an organic solvent. Useful organic solvents include aromatics (especially xylenes) and petroleum fractions (especially the high boiling naphthalene and olefin portions of petroleum, such as heavy aromatic naphtha). Other solvents may include vegetable oils, seed oils, and esters of vegetable oils and seed oils. Suitable emulsifiers for oil dispersions are selected from conventional anionic and nonionic surfactants. Thickeners or gelling agents are added in the formulation of oil dispersions to modify the rheology or flow characteristics of the liquid and to prevent separation and settling of the dispersed particles or droplets.
The pesticide may also be applied in the form of a particulate composition which is particularly useful for application to soil. Particulate compositions typically contain from about 0.5% to about 10% by weight of a pesticide dispersed in a carrier comprising clay or similar material. Such compositions are typically prepared by dissolving the pesticide in a suitable solvent and applying it to a particulate carrier which has been preformed to an appropriate particle size of from about 0.5mm to about 3 mm. Such compositions may also be formulated by making a cohesive mass or paste of the carrier and molecules and then pressing and drying to obtain the desired particle size. Another form of particle is water Emulsifiable Granules (EG). It is a formulation consisting of granules to be applied in the form of conventional oil-in-water emulsions in which one or more active ingredients are dissolved or diluted in an organic solvent after disintegration and dissolution in water. Water emulsifiable granules comprise one or several active ingredients dissolved or diluted in a suitable organic solvent, said one or several active ingredients being absorbed in a water soluble polymer shell or some other type of soluble or insoluble matrix.
Dusts containing pesticides are prepared by intimately mixing the pesticide in powder form with a suitable dusty agricultural carrier (e.g. kaolin, ground volcanic rock, etc.). The powder may suitably contain from about 1% to about 10% of the pesticide. The powders may be applied in the form of seed dressing or in the form of foliar application using a duster.
It is also practical to apply pesticides in solution in a suitable organic solvent (usually petroleum), such as spray oils which are widely used in agrochemicals.
The pesticide may also be applied in the form of an aerosol composition. In such compositions, the pesticide is dissolved or dispersed in a carrier that is a propellant mixture that generates pressure. The aerosol composition is packaged in a container that dispenses the mixture through an atomizing valve.
When the pesticide is mixed with the food or the attractant or both, a pesticide bait is formed. When pests eat bait, they also eat pesticides. The bait may be in the form of granules, gels, flowable powders, liquids, or solids. The bait may be used for pest refuge.
Fumigants are pesticides that have a relatively high vapor pressure and therefore can be present in the form of a gas at sufficient concentration to kill pests in soil or enclosed spaces. The toxicity of fumigants is proportional to their concentration and exposure time. They are characterized by good diffusion capacity and function by penetrating the respiratory system of the pests or by absorption via the epidermis of the pests. Fumigants are applied to control valley pests (stored product pest) under airtight sheets, in air-tight enclosures or buildings or in special chambers.
Pesticides can be microencapsulated by suspending pesticide particles or droplets in various types of plastic polymers. Microcapsules of various sizes, solubilities, wall thicknesses, and degrees of penetration can be formed by varying the chemistry of the polymer or by varying factors in processing. These factors govern the rate of release of the active ingredient within, which in turn affects the residual performance, speed of action, and odor of the product. The microcapsules may be formulated as suspension concentrates or water dispersible granules.
The oil solution concentrate is made by dissolving the pesticide in a solvent that will keep the pesticide in solution. Oil solutions of pesticides generally break down and kill pests faster than other formulations because the solvent itself has a pesticidal effect and the dissolution of the wax covering the skin increases the rate of pesticide uptake. Other advantages of oil solutions include better storage stability, better crevice permeability, and better adhesion to grease surfaces.
Another embodiment is an oil-in-water emulsion, wherein the emulsion comprises oily beads each having a lamellar liquid crystalline coating and dispersed in an aqueous phase, wherein each oily bead comprises at least one agriculturally active molecule and is individually coated with a monolayer or multilayer layer comprising: (1) at least one nonionic lipophilic surfactant, (2) at least one nonionic hydrophilic surfactant, and (3) at least one ionic surfactant, wherein the beads have an average particle size of less than 800 nanometers.
Other formulation Components
Typically, when the molecules disclosed in formula one are used in formulations, such formulations may also contain other components. These components include, but are not limited to (this is a non-exhaustive and non-mutually exclusive list) wetting agents, spreading agents, sticking agents, penetrating agents, buffering agents, chelating agents, sheeting agents, compatibilizing agents, antifoaming agents, cleaning agents, and emulsifying agents. Several components are described next.
Wetting agents are substances that, when added to a liquid, increase the spreading or penetration power of the liquid by reducing the surface tension between the liquid and the surface on which it is spread. Wetting agents are used in agrochemical formulations for two main functions: during processing and manufacturing, increasing the rate of wetting of the powder in water to produce a soluble liquid or suspension concentrate; and reducing the wetting time of wettable powders and improving the penetration of water into water dispersible granules during mixing of the product with water in a spray tank. Examples of wetting agents for wettable powders, suspension concentrates and water-dispersible granule formulations are: sodium lauryl sulfate, sodium dioctyl sulfosuccinate, alkylphenol ethoxylates, and aliphatic alcohol ethoxylates.
Dispersants are substances that adsorb on the surface of particles, helping to maintain the dispersed state of the particles and preventing them from reaggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture and to ensure that the particles are redispersed in water in a spray tank. They are widely used in wettable powders, suspension concentrates, and water dispersible granules. Surfactants used as dispersants have the ability to adsorb strongly on the particle surface and provide a charged or steric barrier to particle reaggregation. The most commonly used surfactants are anionic surfactants, nonionic surfactants, or mixtures of the two types. For wettable powder formulations, the most common dispersant is sodium lignosulfonate. For suspension concentrates, very good adsorption and stability is obtained using polyelectrolytes, such as sodium naphthalene sulfonate formaldehyde condensates. Tristyrylphenol ethoxylate phosphate esters are also used. Nonionic surfactants such as alkylaryl ethylene oxide condensates and EO-PO block copolymers are sometimes used in suspension concentrates in combination with anionic surfactants as dispersants. In recent years, new very high molecular weight polymeric surfactants have been developed as dispersants. It has a very long hydrophobic "backbone" and a large number of ethylene oxide chains, forming the "teeth" of a "comb" surfactant. These high molecular weight polymers can impart very good long-term stability to the suspension concentrate, since the hydrophobic backbone has many anchor points on the particle surface. Examples of dispersants for agrochemical formulations are: sodium lignosulfonates, sodium naphthalene sulfonate formaldehyde condensates, tristyrylphenol ethoxylate phosphate esters, aliphatic alcohol ethoxylates, alkyl ethoxylates, EO-PO block copolymers, and graft copolymers.
Emulsifiers are substances that stabilize a suspension of droplets of one liquid phase in another liquid phase. In the absence of an emulsifier, the two liquids may be separated into two immiscible liquid phases. The most commonly used emulsifier blends contain an alkylphenol or aliphatic alcohol having twelve or more ethylene oxide units and an oil-soluble calcium salt of dodecyl benzene sulfonate. A hydrophilic lipophilic balance ("HLB") value of from about 8 to about 18 will normally provide a good stable emulsion. Emulsion stability can sometimes be improved by adding small amounts of EO-PO block copolymer surfactant.
Solubilizers are surfactants that will form micelles in water at a concentration above the critical micelle concentration. The micelles are then able to dissolve or solubilize the water-insoluble material within the hydrophobic portion of the micelle. The types of surfactants commonly used for solubilization are nonionic surfactants: sorbitan monooleate; sorbitan monooleate ethoxylate; and methyl oleate.
Surfactants are sometimes used alone or with other additives (such as mineral or vegetable oils) as adjuvants for spray tank mixing to improve the biological performance of the pesticide on the target. The type of surfactant used for bioaugmentation generally depends on the nature and mode of action of the pesticide. However, they are typically nonionic surfactants such as: alkyl ethoxylates, linear aliphatic alcohol ethoxylates, and aliphatic amine ethoxylates.
Carriers or diluents in agricultural formulations are materials that are added to pesticides to give the desired concentration of the product. The carrier is typically a material with a high absorption capacity, while the diluent is typically a material with a low absorption capacity. Carriers and diluents are used in the formulation of dusts, wettable powders, granules, and water dispersible granules.
Organic solvents are mainly used to formulate emulsifiable concentrates, oil-in-water emulsions, suspoemulsions, oil dispersions and ultra low volume formulations, and to a lesser extent, particle formulations. Sometimes solvent mixtures are used. The first main group of solvents is aliphatic paraffinic oils, such as kerosene or refined paraffin. The second main group (and most commonly used) of solvents includes aromatic solvents such as xylene and higher molecular weight C9 and C10 aromatic solvent fractions. Chlorinated hydrocarbons may be used as co-solvents to prevent crystallization of the pesticide when the formulation is emulsified in water. Alcohols are sometimes used as cosolvents to increase solvency. Other solvents may include vegetable oils, seed oils, and esters of vegetable oils and seed oils.
Thickeners or gelling agents are used primarily to formulate suspension concentrates, oil dispersions, emulsions and suspoemulsions to modify the rheological or flow characteristics of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickeners, gelling agents and anti-settling agents generally fall into two categories, namely water-insoluble particles and water-soluble polymers. Clay and silica can be used to prepare suspension concentrates and oil dispersion formulations. Examples of these types of materials include, but are not limited to, montmorillonite, bentonite, magnesium aluminum silicate, and attapulgite. Water-soluble polysaccharides in aqueous suspension concentrates have been used as thickening-gelling agents for many years. The most common types of polysaccharides are natural extracts of seeds and seaweeds or synthetic derivatives of cellulose. Examples of these types of materials include, but are not limited to, guar gum, locust bean gum, carrageenan, alginates, methylcellulose, sodium carboxymethylcellulose (SCMC), and Hydroxyethylcellulose (HEC). Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohols, and polyethylene oxides. Another good anti-settling agent is xanthan gum.
Microorganisms can cause spoilage of formulated products. Thus, the use of preservatives eliminates or reduces their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt, sorbic acid and its sodium or potassium salt, benzoic acid and its sodium salt, sodium parahydroxybenzoate, methylparaben, and 1, 2-benzisothiazolin-3-one (BIT).
The presence of surfactants typically causes the water-based formulation to foam during the mixing operation in production and application through spray tanks. To reduce the tendency to foam, a defoamer is typically added during the production phase or prior to filling into the bottle. Generally, there are two types of defoamers, namely silicone and non-silicone. Silicones are typically aqueous emulsions of dimethylpolysiloxanes, while non-silicone defoamers are water-insoluble oils (such as octanol and nonanol) or silica. In both cases, the function of the defoamer is to displace the surfactant from the air-water interface.
"Green" agents (e.g., adjuvants, surfactants, solvents) can reduce the overall environmental footprint of the crop protection formulation. The green agent is biodegradable and is typically derived from natural and/or sustainable sources, such as plant sources and animal sources. Specific examples are: vegetable oils, seed oils, and esters thereof, and alkoxylated alkyl polyglucosides.
Applications of
The molecule of formula one can be applied to any location. Specific sites for application of such molecules include alfalfa, almond, apple, barley, legumes, canola, corn, cotton, crucifers, flowers, forage species (ryegrass, Sudan Grass (Sudan Grass), Tall Fescue (Tall Fescue), Kentucky Blue Grass (Kentucky Blue Grass) and clover), fruit, lettuce, oat, oilseed crops, citrus, peanut, pear, pepper, potato, rice, sorghum, soybean, strawberry, sugarcane, sugar beet, sunflower, tobacco, tomato, Wheat (e.g., Hard Red Winter Wheat (Hard Red Winter Wheat), Soft Red Winter Wheat (Soft Red Winter Wheat), White Winter Wheat (White Winter Wheat), Hard Red Spring Wheat (Hard Red Spring Wheat) and lunu Spring Wheat (Durum Spring Wheat)) and the growth of other seeds or the locus where such seeds are to be planted.
The molecule of formula one may also be applied where plants (such as crops) are growing and where there is a small amount (even virtually no) of a pest that can commercially harm such plants. The application of such molecules at such locations would be beneficial for plant growth at such locations. Such benefits may include, but are not limited to: a better root system for helping the plant to grow; helping the plant to better withstand stress growth conditions; improving the health of the plant; increasing the yield of the plant (e.g., increasing biomass and/or increasing the content of valuable components); improving the vigor of the plant (e.g., improving plant growth and/or making the leaves greener); improving the quality of a plant (e.g., improving the content or composition of certain ingredients); and improving tolerance of a plant to abiotic and/or biotic stress.
When growing a variety of plants, the molecule of formula one may be used with ammonium sulfate as this may provide additional benefits.
The molecule of formula one may be applied on, in or around the following plants: genetically modified to express a particular trait (e.g., bacillus thuringiensis (e.g., Cry1Ab, Cry1Ac, Cry1Fa, cry1a.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Ab1/Cry35Ab1)), plants expressing other insecticidal toxins, or plants expressing herbicide tolerance, or plants having "stacked" exogenous genes expressing insecticidal toxins, herbicide tolerance, nutritional enhancements, or any other beneficial trait.
The molecule of formula one may be applied to foliage and/or fruiting parts of a plant to control pests. Such molecules will be in direct contact with pests, or pests will consume such molecules when consuming the plant or when drawing the plant's juice or other nutrients.
The molecule of formula one may also be applied to soil and when applied in this manner, pests that eat roots and stems can be controlled. The roots can absorb such molecules, thereby delivering them up the foliar parts of the plant to control pests chewing on the ground and eating the sap.
Systemic movement of pesticides in plants can be used to control pests on one part of a plant by applying the molecule of formula one to a different part of the plant (e.g., by spraying the locus). For example, control of foliar-feeding insects can be achieved by drip irrigation or furrow application, by treating the soil with, for example, pre-or post-planting soil drench, or by treating the plant seeds prior to planting.
The molecule of formula one may be used with a bait. Typically for baits, the bait is placed on a ground surface where, for example, termites can contact and/or be attracted to the bait. Baits may also be applied to surfaces (horizontal, vertical or inclined surfaces) of buildings where, for example, ants, termites, cockroaches and flies may come into contact with and/or be attracted to the bait.
The molecule of formula one may be encapsulated inside the capsule or placed on the surface of the capsule. The size of the capsules may range from nanometer size (about 100 nm diameter) to micron size (about 10-900 micron diameter).
The molecule of formula one may be applied to an egg of a pest. Because of the unique ability of some pest eggs to resist certain pesticides, it may be desirable to reapply such molecules to control emerging larvae.
The molecule of formula one may be used as a seed treatment. The seed treatment may be applied to all types of seeds, including seeds to be germinated from plants genetically modified to express a particular trait. Representative examples include those expressing proteins or other insecticidal toxins that are toxic to invertebrate pests (e.g., bacillus thuringiensis), those expressing herbicide tolerance (e.g., "Roundup Ready" seeds), or those having "stacked" exogenous genes that express insecticidal toxins, herbicide tolerance, nutritional enhancements, drought resistance, or any other beneficial trait. In addition, such seed treatment agents having a molecule of formula one may further enhance the ability of the plant to better withstand stressed growth conditions. This results in healthier, more viable plants, which may result in higher yields at harvest time. Overall, amounts of about 1 gram to about 500 grams of such molecules per 100,000 seeds are expected to provide good benefits, amounts of about 10 grams to about 100 grams per 100,000 seeds are expected to provide better benefits, and amounts of about 25 grams to about 75 grams per 100,000 seeds are expected to provide even better benefits.
The molecule of formula one may be used with one or more active ingredients in a soil improving agent. The molecules of formula one can be used in the field of veterinary medicine or in the field of non-human animal breeding for controlling endoparasites and ectoparasites. Such molecules can be applied by: orally, e.g. in the form of tablets, capsules, drinks, granules, transdermally, e.g. in the form of dips, sprays, pours, spots and dusts, and parenterally, e.g. in the form of injections.
The molecules of formula one may also be advantageously used in livestock breeding, such as cattle, chickens, geese, goats, pigs, sheep and turkeys. They may also be advantageously used in pets such as horses, dogs and cats. The particular pests to be controlled may be flies, fleas, and ticks that are infested with such animals. Suitable formulations are orally administered to animals along with drinking water or diet. Suitable dosages and formulations depend on the species.
The molecules of formula one may also be used for controlling parasites in the animals listed above, in particular the intestines.
The molecule of formula one may also be used in a therapeutic method of human health care. Such methods include, but are not limited to, oral administration in the form of, for example, tablets, capsules, beverages, granules, and transdermal applications.
The molecule of formula one may also be applied to invasive pests. Pests worldwide have migrated to new environments (for such pests) and have since become new invasive species of such new environments. Such molecules can also be used in such new invasive species to control them in such new environments.
From the above and following table sections, the following details are additionally provided.
1. A molecule having the formula
Wherein:
(A)R1selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(B)R2selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(C)R3selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(D)R4selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(E)R5selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(F)R6is H;
(G)R7selected from the group consisting of: F. cl, and Br;
(H)R8selected from the group consisting of: F. cl, and Br;
(I)R9is H;
(J)Q1selected from the group consisting of O and S;
(K)Q2selected from the group consisting of O and S;
(L)R10selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)1-C3) Alkyl OC (═ O) (C)1-C3) An alkyl group;
(M)R11selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(N)R12selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(O)R13selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(P)R14selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(Q)R15selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Haloalkyl, (C)1-C3) Alkylphenyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl, (C)1-C3) Alkyl OC (═ O) (C)1-C3) Alkyl, and C (═ O) (C)1-C3) An alkyl group;
(R)R16、R17、R18、R19and R20Independently selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、NH2、OH、SF5、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, (C)2-C3) Alkenyl, (C)2-C3) Haloalkenyl, and N (R)21)C(＝O)(R22) Wherein R is16、R17、R18、R19And R20At least one and not more than two of which are N (R)21)C(＝O)(R22)；
(S)R21Selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Haloalkyl, (C)2-C3) Haloalkenyl, (C)1-C3) Alkylphenyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl, (C)1-C3) Alkyl OC (═ O) (C)1-C3) Alkyl, C (═ O) (C)1-C3) Alkyl, and phenyl;
(T)R22selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-aryl, (C)1-C6) alkyl-S (═ O)n-heterocyclyl (C)2-C6) alkenyl-S (═ O)n-(C1-C6) Alkyl, (C)2-C6) alkenyl-S (═ O)n-(C2-C6) Alkenyl, (C)2-C6) alkenyl-S (═ O)n-aryl, (C)2-C6) alkenyl-S (═ O)n-a heterocyclic group,
wherein n is 0, 1, or 2, and
wherein each of said alkyl and alkenyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) Cycloalkyl radicals, and
wherein each of said aryl and heterocyclyl groups may be substituted with one or more substituents selected from the group consisting of: (C)1-C3) Alkyl, F, Cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) A cycloalkyl group; and
n-oxides, agriculturally acceptable acid addition salts, salt derivatives, solvates, ester derivatives, crystalline polymorphs, isotopes, resolved stereoisomers, tautomers, pro-insecticides of a molecule of formula one,
provided that the following molecules are excluded
Molecule F1299.
2. The molecule of detail 1, wherein:
(A)R1selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(B)R2selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(C)R3selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(D)R4selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(E)R5selected from the group consisting ofGroup (b): H. f, Cl, Br, I, CN, NO2、SF5And (C)1-C3) A haloalkyl group;
(F)R6is H;
(G)R7selected from the group consisting of: F. cl, and Br;
(H)R8selected from the group consisting of: F. cl, and Br;
(I)R9is H;
(J)Q1selected from the group consisting of O and S;
(K)Q2selected from the group consisting of O and S;
(L)R10selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)1-C3) Alkyl OC (═ O) (C)1-C3) An alkyl group;
(M)R11selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(N)R12selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(O)R13selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(P)R14selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, and (C)1-C3) An alkoxy group;
(Q)R15selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Haloalkyl, (C)1-C3) Alkylphenyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl, (C)1-C3) Alkyl OC (═ O) (C)1-C3) Alkyl, and C (═ O) (C)1-C3) An alkyl group;
(R)R16、R17、R18、R19and R20Independently selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、NH2、OH、SF5、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, (C)2-C3) Alkenyl, (C)2-C3) Haloalkenyl, and N (R)21)C(＝O)(R22) Wherein R is16、R17、R18、R19And R20At least one and not more than two of which are N (R)21)C(＝O)(R22)；
(S)R21Selected from the group consisting of: H. (C)1-C3) Alkyl, (C)2-C3) Alkenyl, (C)2-C3) Alkynyl, (C)1-C3) Haloalkyl, (C)2-C3) Haloalkenyl, (C)1-C3) Alkylphenyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl, (C)1-C3) Alkyl OC (═ O) (C)1-C3) Alkyl, C (═ O) (C)1-C3) Alkyl, and phenyl;
(T)R22selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-aryl, (C)1-C6) alkyl-S (═ O)n-heterocyclyl (C)2-C6) Alkene(s)radical-S (═ O)n-(C1-C6) Alkyl, (C)2-C6) alkenyl-S (═ O)n-(C2-C6) Alkenyl, (C)2-C6) alkenyl-S (═ O)n-aryl, (C)2-C6) alkenyl-S (═ O)n-a heterocyclic group,
wherein n is 0, 1, or 2, and
wherein each of said alkyl and alkenyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) Cycloalkyl radicals, and
wherein each of said aryl and heterocyclyl groups may be substituted with one or more substituents selected from the group consisting of: (C)1-C3) Alkyl, F, Cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) A cycloalkyl group; and is
Provided that the following molecules are excluded
Molecule F1299.
3. The molecule according to the preceding details 1 and 2, wherein the molecule has the following formula
4. The molecule of any one of the preceding details, wherein R1Selected from the group consisting of: H. f, Cl、Br、SF5And CF3。
5. The molecule of any one of the preceding details, wherein R2Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
6. The molecule of any one of the preceding details, wherein R3Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
7. The molecule of any one of the preceding details, wherein R4Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
8. The molecule of any one of the preceding details, wherein R5Selected from the group consisting of: H. f, Cl, Br, SF5And CF3。
9. The molecule of any one of the preceding details, wherein R2、R3And R4At least one of which is SF5。
10. The molecule of any one of the preceding details, wherein R7Is Cl.
11. The molecule of any one of the preceding details, wherein R8Is Cl.
12. The molecule of any one of the preceding details, wherein R7And R8Is different.
13. The molecule of any one of the preceding details, wherein Q1Is O.
14. The molecule of any one of the preceding details, wherein Q2Is O.
15. The molecule of any one of the preceding details, wherein R10Is H.
16. The molecule of any one of the preceding details, wherein R11Is H.
17. The molecule of any one of the preceding details, wherein R12Selected from the group consisting of: H. f, Cl, CH3And CF3。
18. According to the frontThe molecule of any one of the preceding details, wherein R13Selected from the group consisting of: F. cl, CH3And OCH3。
19. The molecule of any one of the preceding details, wherein R14Selected from the group consisting of: H. f, and Cl.
20. The molecule of any one of the preceding details, wherein R15Is H.
21. The molecule of any one of the preceding details, wherein:
(a)R16、R18、R19and R20Independently selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、NH2、OH、SF5、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, (C)2-C3) Alkenyl group, and (C)2-C3) Haloalkenyl, and R17Is N (R)21)C(＝O)(R22) (ii) a Or
(b)R16、R17、R19And R20Independently selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、NH2、OH、SF5、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, (C)2-C3) Alkenyl group, and (C)2-C3) Haloalkenyl, and R18Is N (R)21)C(＝O)(R22)。
22. The molecule of any one of the preceding details, wherein R21Is H.
23. The molecule of any one of the preceding details, wherein:
R1selected from the group consisting of: H. f, Cl, Br, SF5And CF3；
R2Selected from the group consisting of: H. f, Cl, Br, SF5And CF3；
R3Selected from the group consisting of: H. f, Cl, Br, SF5And CF3；
R4Selected from the group consisting of: H. f, Cl, Br, SF5And CF3；
R5Selected from the group consisting of: H. f, Cl, Br, SF5And CF3；
R7Is Cl;
R8is Cl;
Q1is O;
Q2is O;
R10is H;
R11is H;
R12selected from the group consisting of: H. f, Cl, CH3And CF3；
R13Selected from the group consisting of: F. cl, CH3And OCH3；
R14Selected from the group consisting of: H. f, and Cl;
R15is H;
R16、R18、R19and R20Independently selected from the group consisting of: H. f, Cl, Br, I, CN, NO2、NH2、OH、SF5、(C1-C3) Alkyl, (C)1-C3) Haloalkyl, (C)2-C3) Alkenyl group, and (C)2-C3) A haloalkenyl group; and is
R17Is N (R)21)C(＝O)(R22)。
24. The molecule of any one of preceding details, including 1 to 23, wherein R22Selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-aryl, (C)1-C6) alkyl-S (═ O)n-heterocyclyl, wherein n ═ 0, 1, or 2, and whereinEach of the alkyl and alkenyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) Cycloalkyl, and wherein each of said aryl and heterocyclyl groups may be substituted with one or more substituents selected from the group consisting of: (C)1-C3) Alkyl, F, Cl, Br, I, CN, OH, oxo, NO2、NH2、NH(C1-C3) Alkyl, N ((C)1-C3) Alkyl radical)2、O(C1-C6) Alkyl, (C)1-C3) Alkyl O (C)1-C3) Alkyl group, and (C)3-C6) A cycloalkyl group.
25. The molecule of any one of preceding details, including 1 to 23, wherein R22Selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-phenyl, (C)1-C6) alkyl-S (═ O)n-pyridinyl, wherein n ═ 0, 1, or 2, and wherein each of said alkyl and alkenyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, and I, and wherein each of said phenyl and pyridyl groups may be substituted with one or more substituents selected from the group consisting of: F. cl, Br, and I.
26. The molecule of any one of preceding details, including 1 to 23, wherein
R1Is H;
R2selected from the group consisting of: H. f, Cl, and CF3；
R3Selected from the group consisting of: H. f, andCl；
R4selected from the group consisting of: H. f, Cl, and CF3；
R5Is H;
R7is Cl;
R8is Cl;
Q1is O;
Q2is O;
R10is H;
R11is H;
R12is H;
R13is Cl;
R14is H;
R15is H;
R16is F;
R17is N (R)21)C(＝O)(R22)；
R18Is F;
R19is H;
R20is H;
R21is H; and is
R22Selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-phenyl, (C)1-C6) alkyl-S (═ O)n-a pyridyl group,
wherein n is 0, 1, or 2;
wherein each of the alkyl, alkenyl, phenyl, and pyridyl groups may be substituted with one or more substituents selected from the group consisting of F and Cl.
27. The molecule of any one of preceding details, including 1 to 23, wherein
R1Is H;
R2selected from the group consisting of: H. f, Cl, and CF3；
R3Selected from the group consisting of: H. f, and Cl;
R4selected from the group consisting of: H. f, Cl, and CF3；
R5Is H;
R7is Cl;
R8is Cl;
Q1is O;
Q2is O;
R10is H;
R11is H;
R12is H;
R13is Cl;
R14is H;
R15is H;
R16is F;
R17is H;
R18is N (R)21)C(＝O)(R22)；
R19Is H;
R20is H;
R21is H; and is
R22Selected from the group consisting of: (C)1-C6) alkyl-S (═ O)n-(C1-C6) Alkyl, (C)1-C6) alkyl-S (═ O)n-(C2-C6) Alkenyl, (C)1-C6) alkyl-S (═ O)n-phenyl, (C)1-C6) alkyl-S (═ O)n-a pyridyl group,
wherein n is 0, 1, or 2;
wherein each of the alkyl, alkenyl, phenyl, and pyridyl groups may be substituted with one or more substituents selected from the group consisting of F and Cl.
28. A molecule selected from table 2, preferably a molecule selected from the group consisting of: f2, F3, F4, F5, F6, F7, F8, F9, F10, F11, F12, F13, F14, F15, F16, F17, F18, F19, F22, F23, F24, F25, F26, F27, F28, F29, F30, F31, F32, F33, F34, F35, F37, F39, F42, F44, F45, F46, F47, F48, F49, F50, F51, and F52.
29. A molecule selected from table 2, preferably a molecule selected from the group consisting of: f15, F16, F17, F18, F19, F21, F23, F24, F25, F32, F34, and F46.
30. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient.
31. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient selected from the group consisting of: acaricidal agents, algicides, antifeedants, avicides, bactericides, bird repellents, chemosterilants, fungicides, herbicide safeners, herbicides, insect attractants, insect repellents, insecticides, mammal repellents, mating disruptors, molluscicides, nematicides, plant activators, plant growth regulators, rodenticides, synergists, and virucides.
32. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient selected from AIGA.
33. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising tylenepyrrazoflor.
34. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising loratadine.
35. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising a molecule selected from table a.
36. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient selected from AIGA-2.
37. A composition comprising a molecule according to the preceding details, including any one of 1 to 29, further comprising chlorpyrifos.
38. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising hexaflumuron.
39. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising methoxyfenozide.
40. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising a polyfluorourea.
41. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising spinetoram.
42. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising spinosad.
43. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising sulfoxaflor.
44. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient selected from AIGA-3.
45. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising acequinocyl.
46. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising acetamiprid.
47. A composition comprising a molecule according to any of the preceding details, including 1 to 29, further comprising acetofenapyr.
48. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising abamectin.
49. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising methyl valthion.
50. A composition comprising a molecule according to any of the preceding details, including 1 to 29, further comprising a bifenazate.
51. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising bifenthrin.
52. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising carbaryl.
53. A composition comprising a molecule according to the preceding details, including any one of 1 to 29, further comprising carbofuran.
54. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising chlorfenapyr.
55. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising chlorfluazuron.
56. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising chromafenozide.
57. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising clothianidin.
58. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising cyfluthrin.
59. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising cypermethrin.
60. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising deltamethrin.
61. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising diafenthiuron.
62. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising emamectin benzoate.
63. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising endosulfan.
64. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising esfenvalerate.
65. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising ethiprole.
A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising etoxazole.
67. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising fipronil.
68. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising flonicamid.
69. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising fluacrypyrim.
70. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising gamma-cyhalothrin.
71. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising halofenozide.
72. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising indoxacarb.
73. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising lambda-cyhalothrin.
74. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising lufenuron.
75. A composition comprising a molecule according to the preceding detail, including any one of 1 to 29, further comprising malathion.
76. A composition comprising a molecule according to the preceding detail, including any one of 1 to 29, further comprising methomyl.
77. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising a novaluron.
78. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising permethrin.
79. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising pyridalyl.
80. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising fluacrypyrim.
81. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising spirodiclofen.
82. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising tebufenozide.
83. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising thiacloprid.
84. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising thiamethoxam.
85. A composition comprising a molecule according to the preceding detail, including any one of 1 to 29, further comprising thiodicarb.
86. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising tolfenpyrad.
87. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising zeta-cypermethrin.
88. A composition comprising a molecule according to any of the preceding details, including 1 to 29, further comprising a biotinicide.
89. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from an acetylcholinesterase (AChE) inhibitor.
90. A composition comprising a molecule according to any of the preceding details, including 1 to 29, further comprising an active ingredient from a GABA-gated chloride channel antagonist.
91. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a sodium channel modulator.
92. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a nicotinic acetylcholine receptor (nAChR) agonist.
93. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a nicotinic acetylcholine receptor (nAChR) allosteric activator.
94. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a chloride channel activator.
95. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a juvenile hormone mimic.
96. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from an additional non-specific (multi-site) inhibitor.
97. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a sound reactive organ modifier.
98. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a mite growth inhibitor.
99. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient of a microbial interference agent from insect midgut membranes.
100. A composition comprising a molecule according to any of the preceding details, including 1 to 29, further comprising an active ingredient from a mitochondrial ATP synthase inhibitor.
101. A composition comprising a molecule according to any of the preceding details, including 1 to 29, further comprising an active ingredient from an uncoupler which generates oxidative phosphorylation via disruption of proton gradient.
102. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a nicotinic acetylcholine receptor (nAChR) channel blocker.
103. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a type 0 chitin biosynthesis inhibitor.
104. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a type 1 chitin biosynthesis inhibitor.
105. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a dipteran molting disruptor.
106. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from an ecdysone receptor agonist.
107. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from an octopamine receptor agonist.
108. A composition comprising a molecule according to any of the preceding details, including 1 to 29, further comprising an active ingredient from a mitochondrial complex III electron transport inhibitor.
109. A composition comprising a molecule according to any of the preceding details, including 1 to 29, further comprising an active ingredient from a mitochondrial complex I electron transport inhibitor.
110. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a voltage-dependent sodium channel blocker.
111. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from an inhibitor of acetyl CoA carboxylase.
112. A composition comprising a molecule according to any of the preceding details, including 1 to 29, further comprising an active ingredient from a mitochondrial complex IV electron transport inhibitor.
113. A composition comprising a molecule according to any of the preceding details, including 1 to 29, further comprising an active ingredient from a mitochondrial complex II electron transport inhibitor.
114. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from a liarinodin receptor modulator.
115. A composition comprising a molecule according to any one of the preceding details, including 1 to 29, further comprising an active ingredient from group UN.
116. The composition of any of the preceding details, including 30 to 115, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient is from 100:1 to 1: 100.
117. The composition of any of the preceding details, including 30 to 115, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient is from 50:1 to 1: 50.
118. The composition of any of the preceding details, including 30 to 115, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient is 20:1 to 1: 20.
119. The composition of any of the preceding details, including 30 to 115, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient is 10:1 to 1: 10.
120. The composition of any of the preceding details, including 30 to 115, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient is from 5:1 to 1: 5.
121. The composition of any of the preceding details, including 30 to 115, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient is 3:1 to 1: 3.
122. The composition of any of the preceding details, including 30 to 115, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient is from 2:1 to 1: 2.
123. The composition of any of the preceding details, including 30 to 115, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient is 1: 1.
124. The composition of any of the preceding details, including 30 to 115, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient is X: Y; wherein X is the weight part of a molecule of formula one or formula two and Y is the weight part of the active ingredient; further wherein X is present in a weight part range of 0< X.ltoreq.100 and Y is present in a weight part range of 0< Y.ltoreq.100; and further wherein X and Y are selected from table C.
125. The composition of claim 124, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient ranges from X1:Y1To X2:Y2(ii) a Further wherein X1>Y1And X2<Y2。
126. The composition of claim 124, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient ranges from X1:Y1To X2:Y2(ii) a Further wherein X1>Y1And X2>Y2。
127. The composition of claim 124, wherein the weight ratio of the molecule according to formula one or formula two to the active ingredient ranges from X1:Y1To X2:Y2(ii) a Further wherein X1<Y1And X2<Y2。
128. A method of producing a composition, the method comprising mixing a molecule according to any one of the preceding details, including 1 to 29, with one or more active ingredients.
129. Seed treated with a molecule according to any one of the preceding details, including 1 to 29.
130. The molecule according to any one of the preceding details, including 1 to 29, wherein the molecule is in the form of an agriculturally acceptable acid addition salt.
131. The molecule of any one of preceding details, including 1 to 29, wherein the molecule is in the form of a salt derivative.
132. The molecule of any one of claims 1 to 29, wherein the molecule is in the form of a solvate.
133. The molecule of any one of preceding details, including 1 to 29, wherein the molecule is in the form of an ester derivative.
134. The molecule according to any one of the preceding details, including 1 to 29, wherein the molecule is in the form of a crystalline polymorph.
135. The molecule of any one of claims 1 to 29, comprising, in accordance with the preceding details, wherein the molecule has deuterium, tritium, radioactive carbon, or a combination thereof.
136. The molecule of any one of claims 1 to 29, comprising, wherein the molecule is in the form of one or more stereoisomers.
137. The molecule of any one of claims 1 to 29, comprising the molecule in resolved stereoisomeric form.
138. A method of controlling pests, the method comprising applying to a locus a pesticidally effective amount of a molecule according to any of the preceding details, including 1 to 29.
139. A method of controlling pests, the method comprising applying to a locus a pesticidally effective amount of a composition according to any of the foregoing details, including 30 to 115.
140. The method according to details 138 and 139, wherein the pest is selected from the group consisting of: ants, aphids, bed bugs (bed bugs), beetles, moths, caterpillars, cockroaches, crickets, earwigs, fleas, flies, grasshoppers, maggots, leaf hoppers, lice, grasshoppers, maggots, mites, nematodes, plant hoppers, wood lice, leaf bees, scale insects, silverfish, slugs, snails, spiders, springtails, stink bugs, sympodial mites, termites, thrips, ticks, wasps, white flies and ironworms.
141. The method of details 138 and 139, wherein the pest is selected from the lobbies subphyla, the polypod subphyla, or the hexapod subphyla.
142. The method of details 138 and 139, wherein the pest is selected from arachnids, synopsis, or entomophyes.
143. The method according to details 138 and 139, wherein the pest is selected from the order phthiraptera.
144. The method of details 138 and 139, wherein the pest is selected from coleoptera.
145. The method of details 138 and 139, wherein the pest is selected from the order dermaptera.
146. The method of details 138 and 139, wherein the pest is selected from the order blattaria.
147. The method of details 138 and 139, wherein the pest is selected from the order diptera.
148. The method of details 138 and 139, wherein the pest is selected from the order hemiptera.
149. The method of details 138 and 139, wherein the pest is selected from the order hymenoptera.
150. The method of details 138 and 139, wherein the pest is selected from the order isoptera.
151. The method of details 138 and 139, wherein the pest is selected from the order lepidoptera.
152. The method of details 138 and 139, wherein the pest is selected from the order trichophaga.
153. The method of details 138 and 139, wherein the pest is selected from orthoptera.
154. The method of details 138 and 139, wherein the pest is selected from the order rodentia.
155. The method according to details 138 and 139, wherein the pest is selected from the order siphonaptera.
156. The method of details 138 and 139, wherein the pest is selected from the order thysanoptera.
157. The method of details 138 and 139, wherein the pest is selected from the order thysanoptera.
158. The method according to details 138 and 139, wherein the pest is selected from the order acarina.
159. The method of details 138 and 139, wherein the pest is selected from the order arachnida.
160. The method of details 138 and 139, wherein the pest is selected from the synopsis.
161. The method of details 138 and 139, wherein the pest is selected from the subclass Rhabdoviridae.
162. The method of details 138 and 139, wherein the pest is selected from the phylum nematoda.
163. The method of details 138 and 139, wherein the pest is selected from the phylum mollusca.
164. The method according to details 138 and 139, wherein the pest is a sap-feeding pest.
165. The method of details 138 and 139, wherein the pest is selected from the group consisting of aphids, leaf hoppers, moths, scale insects, thrips, psyllids, whiteflies, stink bugs, and whiteflies.
166. The method according to details 138 and 139, wherein the pest is selected from the order phthiraptera and pediculoptera.
167. The method of details 138 and 139, wherein the pest is selected from the group consisting of an agriophyllum species, a cicada species, an aphid species, a whitefly species, an agusticum species, an american stinkbug species, an apolygus species, an elongatus species, an oridonoporus species, and a aphid species.
168. The method of details 138 and 139, wherein the pest is a chewing pest.
169. The method of details 138 and 139, wherein the pest is selected from the group consisting of a caterpillar, a beetle, a grasshopper, and a locust.
170. The method of details 138 and 139, wherein the pest is selected from the group consisting of coleoptera and lepidoptera.
171. The method of details 138 and 139, wherein the pest is selected from the group consisting of a floral weevil species, a watercress species, a kochia species, a diabrotica species, a cephalospora species, a root-leaved beetle species, a leafflower weevil species, a gill-tortoise species, a striped-flea species, a poinsettia species, a rice weevil species.
172. The method of particulars 138 and 139 wherein the locus is an area where alfalfa, almond, apple, barley, legumes, canola, corn, cotton, crucifers, lettuce, oats, citrus, pear, pepper, potato, rice, sorghum, soybean, strawberry, sugarcane, sugar beet, sunflower, tobacco, tomato, wheat, and other commercial crops are growing or are planting their seeds.
173. The method according to details 138 and 139, wherein the locus is a region where genetically modified plants are grown to express a specific trait.
174. The method according to details 138 and 139, wherein the application is to foliar and/or fruiting parts of the plant.
175. The method according to details 138 and 139, wherein the application is to soil.
176. The method according to details 138 and 139, wherein the applying is performed by drip irrigation, furrow application, or pre-or post-planting soil drenching.
177. The method according to details 138 and 139, wherein the application is to foliar and/or fruiting parts of the plant, or by planting seeds of the pre-treated plant.
178. A method comprising applying a molecule according to any of the preceding details, including 1 to 29, to a locus comprising a non-human animal to control endoparasites, ectoparasites, or both.
Headings in this document are for convenience only and should not be used to interpret any portion thereof.
Table section
