Substituted anthranilamides for controlling invertebrate pests

The present invention is free of certain substituted anthranilamides, their N-oxides, salts and compositions suitable for agricultural and non-agricultural applications, including those listed below, and in both agricultural and non-agricultural environments. With respect to their use and use for controlling invertebrate pests.

Control of invertebrate pests is crucial to achieving high produce efficiency. Damage to growing and stored produce by invertebrate pests can cause a significant reduction in productivity, which can result in increased costs for consumers. Control of inverteous pests in forest management, greenhouse crops, ornamental plants, nursery crops, stored food and textiles, livestock, homes, and public and animal health is also important. Many products are commercially available for these purposes, but seek new compounds that are more effective, less expensive, less toxic, environmentally safer, or have different modes of action. The request continues.

Patent Document 1 describes an N-acylanthranilic acid derivative of formula i as an insecticide.

<chemistry num="1"><img file="JP4224397B2_D0001.tif" /></chemistry>

(In the equation, above all, X is a direct bond and Y is H or C.₁-C₆Alkyl, Z is NH₂, NH (C₁-C₃Alkyl) or N (C)₁-C₃Alkyl)₂And R¹From R⁹Independently, H, Halogen, C₁-C₆Alkyl, phenyl, hydroxy, C₁-C₆Alkoxy or C₁-C₇It is acyloxy. ) Is disclosed.

<patcit num="1"><text>NL No. 9,202,078</text></patcit>

<p> The present invention is in formula I</p><p><chemistry num="2"><img file="JP4224397B2_D0002.tif" /></chemistry></p><p>(During the ceremony, A and B are independently O or S, X is N or CR¹⁰And Y is N or CH, R¹Is H; R¹¹; Or each, in some cases R⁶, Halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino, (C₁-C₄Alkyl) C₃-C₆Cycloalkylamino and R¹¹May be substituted with one or more substituents selected from the group consisting of C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne or C₃-C₆Cycloalkyl, R²Is H, C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne, C₃-C₆Cycloalkyl, C₁-C₄Alkoxy, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino, (C₁-C₄Alkyl) C₃-C₆Cycloalkylamino, C₂-C₆Alkoxycarbonyl or C₂-C₆Alkylcarbonyl, R³Is H; R¹¹; Or each, in some cases R⁶, Halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₃-C₆Trialkylsilyl, R¹¹, Each ring may be substituted with 1 to 3 substituents selected independently of W and optionally 1 R¹²May be substituted with one or more substituents selected from the group consisting of phenyl, phenoxy and 5- or 6-membered aromatic heterocycles optionally substituted with C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne or C₃-C₆Cycloalkyl or R²And R³Can form K together with the nitrogen they are bound to, R⁴Is C₁-C₄Alkyl, C₁-C₄Haloalkyl, CN, halogen, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄It is a haloalkyl sulfonyl and R⁵And R⁸Are independent of each other, H; C₁-C₄Alkyl; C₁-C₄Halogen; Halogen; R¹²; G; J; OJ; OG; S (O)_p-J; S (O)_p-G; May be substituted with 1 to 3 substituents selected independently of W and optionally 1 R¹²May be replaced by S (O)_p-Phenyl; G, J, R respectively⁶, Halogen, CN, NO₂, NH₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄Haloalkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Trialkylsilyl, each ring may be substituted with 1 to 3 substituents selected independently of W and optionally 1 R¹²C substituted with one or more substituents selected from the group consisting of a phenyl ring and a phenoxy ring optionally substituted with₁-C₁₀Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne, C₁-C₄Alkoxy or C₁-C₄Alkylthio Each G is independent, C (= O), SO or S (O)₂Arbitrarily contains one or two ring elements selected from the group consisting of and optionally C₁-C₂Alkyl, halogen, CN, NO₂And C₁-C₂It is a 5- or 6-membered non-aromatic heterocycle, which may be substituted with 1 to 4 substituents selected from the group consisting of alkoxy, or Each G is independent, C₂-C₆Alkenyl, C₂-C₆Alkyne, each cycloalkyl, (alkyl) cycloalkyl and (cycloalkyl) alkyl may optionally be substituted with one or more halogens C₃-C₇Cycloalkyl, (cyano) C₃-C₇Cycloalkyl, (C₁-C₄Alkyl) C₃-C₆Cycloalkyl, (C₃-C₆Cycloalkyl) C₁-C₄Alkyl Each J may be independently substituted with 1 to 3 substituents selected independently of W and optionally R.¹²A 5- or 6-membered aromatic heterocycle optionally substituted with, Each R⁶Independently, R¹⁹C (= E)-, R¹⁹C (= E) L-, R¹⁹LC (= E)-, (R¹⁹) LC (= E) L-, -O (Q =) P (OR)¹⁹)₂, -SO₂LR¹⁸, Or R¹⁹SO₂L- Each E is independent, O, S, NR¹⁵, NOR¹⁵, NN (R¹⁵)₂, NS = O, N-CN or N-NO₂And R⁷Is H, C₁-C₄Alkyl, C₁-C₄Haloalkyl, halogen, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄It is a haloalkyl sulfonyl and R⁹Is CF₃, OCF₃, OCHF₂, OCH₂CF₃, S (O)_pCF₃, S (O)_pCHF₂Or halogen, R¹⁰Is H, C₁-C₄Alkyl, C₁-C₄Haloalkyl, halogen, CN or C₁-C₄It is haloalkoxy and Each R¹¹Independently C₁-C₆Alkylthio; C₁-C₆Alkyl sulphenyl; C₁-C₆Haloalkylthio; C₁-C₆Haloalkyl sulphenyl; phenylthio or phenylsulphenyl, respectively, optionally substituted with 1 to 3 substituents selected independently of W; (R)¹⁶)₂NS (O)_n-; R¹³C (= O)-; R¹⁴C (= O) L-; R¹⁴LC (= O) S-; R¹³LC (= O)-; R¹³C (= O) NR¹³S (O)_n-; R¹⁴LC (= O) NR¹³S (O)_n-Or R¹⁴LSO₂NR¹³S (O)_n-And Each L is independent, O, NR¹⁸Or S Each R¹²Independently, B (OR¹⁷)₂, NH₂, SH, Thiosianato, C₃-C₈Trialkylsilyloxy, C₁-C₄Alkyl disulfide, SF₅, R¹⁹C (= E)-, R¹⁹C (= E) L-, R¹⁹LC (= E)-, (R¹⁹) LC (= E) L-, -OP (= Q) (OR¹⁹)₂, -SO₂LR¹⁹, R¹⁹SO₂L- Q is O or S Each R¹³Independently, hydrogen; each, in some cases R⁶, Halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino and (C₁-C₄Alkyl) C₃-C₆C may be substituted with one or more substituents selected from the group consisting of cycloalkylaminos₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne or C₃-C₆Cycloalkyl, Each R¹⁴Are, in some cases, R⁶, Halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino and (C₁-C₄Alkyl) C₃-C₆C may be substituted with one or more substituents selected from the group consisting of cycloalkylaminos₁-C₂₀Alkyl, C₂-C₂₀Alkenyl, C₂-C₂₀Alkyne or C₃-C₆Cycloalkyl; or optionally substituted with 1 to 3 substituents selected independently of W and optionally R¹²Phenyl which may be substituted with Each R¹⁵Independently H; C₁-C₆Haloalkyl; possibly CN, NO₂, R⁶, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄Haloalkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylcarbonyl, C₃-C₆It may be substituted with trialkylsilyl, and optionally 1 to 3 substituents selected independently of W, and optionally 1 R.¹²May be substituted with one or more substituents selected from the group consisting of phenyl rings optionally substituted with C₁-C₆Alkyl; or may be substituted with 1 to 3 substituents selected independently of W and optionally R¹²Phenyl which may be substituted with N (R¹⁵)₂Can form K together, R¹⁶Is C₁-C₁₂Alkyl or C₁-C₁₂Haloalkyl or N (R¹⁶)₂Can form K together, Each R¹⁷Is independently H or C₁-C₄Alkyl or B (OR¹⁷)₂May be methyl or C₂-C₆A chain of two to three carbon atoms, which may be substituted with one or two substituents selected independently of the alkoxycarbonyl, can form a ring in which two oxygen atoms are linked. Each R¹⁸Independently, H, C₁-C₆Alkyl or C₁-C₆Haloalkyl or N (R¹³) (R¹⁸) Can form K together, Each R¹⁹Independently H; in some cases CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄Haloalkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, CO₂H, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylcarbonyl, C₃-C₆Substituent with one or more substituents selected from the group consisting of trialkylsilyls and optionally 1 to 3 substituents selected independently of W and optionally a phenyl ring. May be C₁-C₆Alkyl; C₁-C₆Haloalkyl; C₃-C₆Cycloalkyl; or phenyl or pyridinyl, optionally substituted with 1 to 3 substituents selected independently of W. Each K is a substituent pair R¹³And R¹⁸, (R¹⁵)₂Or (R¹⁶)₂Is a ring that may contain 2 to 6 carbon atoms and optionally an additional nitrogen, sulfur or oxygen atom in addition to the nitrogen atom to which the ring is attached, which ring is optionally C.₁-C₂Alkyl, halogen, CN, NO₂And C₁-C₂It may be substituted with 1 to 4 substituents substituted from the group consisting of alkoxy. Each W is independent, C₁-C₄Alkyl, C₂-C₄Alkenyl, C₂-C₄Alkyne, C₃-C₆Cycloalkyl, C₁-C₄Haloalkyl, C₂-C₄Haloalkenyl, C₂-C₄Halo alkynyl, C₃-C₆Halocycloalkyl, halogen, CN, NO₂, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino, (C₁-C₄Alkyl) C₃-C₆Cycloalkylamino, C₂-C₄Alkylcarbonyl, C₂-C₆Alkoxycarbonyl, CO₂H, C₂-C₆Alkylaminocarbonyl, C₃-C₈Dialkylaminocarbonyl or C₃-C₆Trialkylsilyl, Each n is independently 0 or 1 and Each p is 0, 1 or 2 independently, However, (a) R⁵Is H, C₁-C₆Alkyl, C₁-C₆Haloalkyl, C₂-C₆Haloalkenyl, C₂-C₆Halo alkynyl, C₁-C₄Haloalkoxy, C₁-C₄Haloalkylthio or halogen and (b) R⁸Is H, C₁-C₆Alkyl, C₁-C₆Haloalkyl, C₂-C₆Haloalkenyl, C₂-C₆Halo alkynyl, C₁-C₄Haloalkoxy, C₁-C₄Haloalkylthio, halogen, C₂-C₄Alkylcarbonyl, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylaminocarbonyl or C₃-C₈In the case of dialkylaminocarbonyl, (c) R⁶, R¹¹And R¹²There is at least one substituent selected from the group consisting of, and (d) R¹²At least one R if does not exist⁶Or R¹¹Is C₂-C₆Alkylcarbonyl, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylaminocarbonyl and C₃-C₈Other than dialkylaminocarbonyl. ) With respect to the compounds of, and their N-oxides and salts.</p><p> The present invention is also a method of controlling invertebrate pests, which is a biologically effective amount of a compound of formula I, an N-oxide thereof or a salt thereof (eg, the present specification). It also relates to methods comprising contacting with (such as the compositions described in the book). The present invention also presents in a biologically effective amount of an invertebrate pest or environment thereof, a compound of formula I, its N-oxide or salt thereof, or the compound, its N-oxide or salt thereof, and. It also relates to such a method of being contacted with a composition comprising a biologically effective amount of at least one additional compound or drug for controlling an invertent pest.</p><p> The invention also presents at least one addition selected from the group consisting of biologically effective amounts of compounds of formula I, their N-oxides or salts thereof and surfactants, solid diluents and liquid diluents. It also relates to compositions for controlling invertent pests, including constituents. The present invention also comprises a biologically effective amount of a compound of formula I, an N-oxide thereof or a salt thereof and an effective amount of at least one additional biologically active compound or agent. Also related to the composition.</p>

In the above detail, "alkyl" used alone or in compound terms such as "alkylthio" or "haloalkyl" refers to methyl, ethyl, n-propyl, i-propyl, or different butyls. , Pentyl or hexyl isomers, such as linear or branched alkyl. "Alkenes" include 1-propenyl, 2-propenyl, as well as linear or branched alkenes such as different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propazienyl and 2,4-hexadienyl. "Alkynyl" includes 1-propynyl, 2-propynyl, and linear or branched alkynes such as different butynyl, pentynyl and hexynyl isomers. The "alkynyl" can also include a moiety consisting of multiple triple bonds such as 2,5-hexadynyl. "Alkoxy" includes, for example, methoxy, ethoxyn-propyloxy, isopropyloxy and different butoxy, pentoxy and hexyloxy isomers. "Alkylthio" includes methylthio, ethylthio, and linear or branched alkylthio moieties such as different propylthio and butyrichio isomers. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties attached to linear or branched alkyl groups. Examples of "alkylcycloalkyl" include methylcyclopropyl, dimethylcyclopropyl, ethylcyclopentyl, and other cycloalkyl moieties with linear or branched alkyl groups as substituents. "Trialkylsilyl" includes (CH₃)₃Si, (CH₃CH₂)₃Si and [(CH₃)₃C] (CH₃)₂Si is included. "Cycloalkylamino" means that an aminonitrogen atom is attached to a cycloalkyl group and a hydrogen atom, and includes groups such as cyclopropylamino, cyclobutylamino, cyclopentylamino and cyclohexylamino. "(Alkyl) cycloalkylamino" means a cycloalkylamino group in which a hydrogen atom is replaced by an alkyl group, for example (methyl) cyclopropylamino, (ethyl) cyclobutylamino, (isopropyl) cyclopentylamino and Examples include (methyl) cyclohexylamino. As shown in "Means for Solving Problems", cycloalkyl in cycloalkylamino and (alkyl) cycloalkylamino is C.₃-C₆Although it is a cycloalkyl, the alkyl in the (alkyl) cycloalkylamino is C.₁-C₄It is alkyl.

The term "aromatic" indicates that each of the ring atoms is essentially coplanar and has a p-orbital perpendicular to the ring plane, in which (4n + 2) π electrons (n is 0 or positive). (If it is an integer of) satisfies the Hueckel law in relation to the ring. The term "aromatic ring system" means a completely unsaturated carbocycle and heterocycle in which at least one ring of the polycyclic ring system is aromatic. Aromatic carbocyclic rings or fused carbon bicyclic systems include fully aromatic carbocycles in which at least one ring of the polycyclic ring system is aromatic (eg, phenyl, naphthyl and 1,2,3, 4-Tetrahydronaphthyl) is included. The term "non-aromatic carbocyclic ring" means a fully saturated carbocycle as well as a partially or completely unsaturated carbocycle in which the Hueckel law is not satisfied by the ring. In connection with the ring or ring system, the term "hetero" is one to four in which at least one ring atom is independently selected from the group consisting of nitrogen, oxygen and sulfur rather than carbon. Heteroatoms can be contained, but each ring is associated with a ring or ring system containing no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. In the terms "heteroaromatic ring or ring system" and "aromatic fused heterobicyclic ring system", at least one ring of a fully aromatic heterocycle and a polycyclic ring system is aromatic (here). , Aromatic includes heterocycles (indicating that the Hueckel law is satisfied). The term "non-aromatic heterocycle or ring system" refers to a fully saturated heterocycle as well as a partially or completely unsaturated heterocycle in which the Hueckel law is not satisfied by any of the rings in the ring system. means. Heterocycles or ring systems can be attached through any available carbon or nitrogen by substitution of hydrogen on carbon or nitrogen.

The term "halogen" includes fluorine, chlorine, bromine or iodine, either alone or in a compound term such as "haloalkyl". Further, when used in a compound term such as "haloalkyl", the alkyl may be partially or completely substituted with halogen atoms which may be the same or different. An example of "haloalkyl" is F₃C, ClCH₂, CF₃CH₂And CF₃CCl₂Can be mentioned. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", "halocycloalkyl" and the like are defined similar to the term "haloalkyl". An example of "haloalkenyl" is (Cl)₂C = CHCH₂And CF₃CH₂CH = CHCH₂Can be mentioned. Examples of "haloalkynyl" include HCCCHCl, CF₃CC, CCl₃CC and FCH₂CCCH₂Can be mentioned. An example of "haloalkoxy" is CHF₂O, CF₃O, CCl₃CH₂O, HCF₂CH₂CH₂O and CF₃CH₂O is mentioned.

An example of "alkylcarbonyl" is C (O) CH₃, C (O) CH₂CH₂CH₃And C (O) CH (CH)₃)₂Can be mentioned. An example of "alkoxycarbonyl" is CH₃OC (= O), CH₃CH₂OC (= O), CH₃CH₂CH₂OC (= O), (CH₃)₂CHOC (= O) and different butoxy- or pentoxycarbonyl isomers can be mentioned. An example of "alkylaminocarbonyl" is CH₃NHC (= O), CH₃CH₂NHC (= O), CH₃CH₂CH₂NHC (= O), (CH₃)₂CHNHC (= O) and different butylmamino- or pentylaminocarbonyl isomers can be mentioned. An example of "dialkylaminocarbonyl" is (CH₃)₂NC (= O), (CH₃CH₂)₂NC (= O), CH₃CH₂(CH₃) NC (= O), CH₃CH₂CH₂(CH₃) NC (= O) and (CH₃)₂CHN (CH₃) C (= O).

The total number of carbon atoms in the substituent is "C"_i-C_jIndicated by numbers, where i and j are integers from 1 to 20. For example, C₁-C₃Alkylsulfonyls range from methylsulphonyls to propylsulphonyls.

In the above detail, if the compound of formula I contains a heterocycle, all substituents are attached to this ring through any available carbon or nitrogen by substitution of hydrogen on carbon or nitrogen.

If a compound is substituted with a substituent having a subscript indicating that it can exceed 1, which indicates the number of substituents, then the substituent (if they exceed 1) is the defined group of substituents. Is selected independently of. In addition, subscript numbers range, eg (R)_ijIf, the number of substituents may be selected from an integer between j, including i and j.

The term "possibly substituted" indicates that the moieties may be substituted or unsubstituted. For example, the term "may be optionally substituted with 1 to 3 substituents" may be a non-replacement of the part, or 1 to 3 available locations on the part may be substituted. Show that it is also good. Substituents whose moieties can be hydrogen, such as R¹Or R⁵Therefore, if this substituent is considered hydrogen, it is perceived to be equivalent to the moiety being unsubstituted.

The compounds of the present invention can exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Those skilled in the art may be more active and / or exhibit beneficial effects when one stereoisomer is richer than or separated from other stereoisomers. I will admit that it may be. In addition, experts know how to separate, enrich, and / or selectively produce said stereoisomers. Thus, the compounds of the invention may exist as a mixture of stereoisomers, as individual stereoisomers, or as optically active forms. Some compounds of the invention can exist as one or more tautomers, and all tautomers of such compounds are part of the invention. Thus, the compounds of the invention may exist as a mixture of tautomers or as individual tautomers.

The present invention includes compounds selected from Formula I, its N-oxides and salts. Those skilled in the art will recognize that not all nitrogen-containing heterocycles can form N-oxides, as nitrogen requires available lone electron pairs for oxidation to oxides. Those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize that tertiary amines can form N-oxides. Complex with peroxy acids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxirane such as dimethyldioxirane. Synthetic methods for the production of N-oxides of heterocyclic and tertiary amines, including oxidation of rings and tertiary amines, are very well known by those skilled in the art. These methods for the production of N-oxides have been extensively described and reviewed in the literature, for example, TL Gilchrist, "Comprehensive Organic". Synthesis, Vol. 7, pp. 748-750, edited by SVLey, Pergamon Press; M. Tisler and B. Stanovnik, " Comprehensive Heterocyclic Chemistry, Volume 3, pp. 18-19, edited by AJ Boulton and A. McKillop, Pergamon Press; MR Grimmett) and BRT Keene, Advances in Heterocyclic Chemistry, Vol. 43, pp. 139-151, edited by ARK Tritzky, Academic Press. M. Tisler and B. Stanovnik "Advances in Heterocyclic" Chemistry, Vol. 9, pp. 285-291, edited by ARK Tritzky and AJ Boulton, Academic Press; and G. W. Etch. GWH Cheeseman and ESGWerstiuk, Advances in Heterocyclic Chemistry, Vol. 22, pp. 390-392, AR Katritzky and A. See Academic Press, edited by AJ Boulton.

The salts of the compounds of the present invention include hydrobromic acid, hydrochlorite, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, etc. Includes acid addition salts with inorganic or organic acids such as 4-toluenesulfonic acid or valerate. The salts of the compounds of the invention also include organic bases (eg, pyridine, ammonia, or triethylamine) or inorganic bases (eg, sodium, potassium, lithium, etc.) if the compound contains acidic moieties such as carboxylic acids or phenols. It also includes those formed of calcium, magnesium or barium hydrides, hydroxides, or carbonates).

The following are preferred for reasons of better activity and / or ease of synthesis. Priority 1. Compound of formula I (in formula, A and B are both O, J is optionally substituted with 1 to 3 substituents in which each J ring is optionally selected independently of W, R¹²A 5- or 6-membered aromatic heterocycle selected from the group consisting of J-1, J-2, J-3 and J-4, optionally substituted with.

<chemistry num="3"><img file="JP4224397B2_D0003.tif" /></chemistry>

Q¹Is O, S or NW, and W¹, X¹, Y¹, Z¹Is independently N or CW, but in J-3 and J-4 W¹, X¹, Y¹Or Z¹At least one of them is N).

Priority 2. R⁶, R¹¹And R¹²A preferred 1 compound in which there is one substituent substituted from the group consisting of.

Priority 3. Preferred 2 compounds of formula Is.

<chemistry num="4"><img file="JP4224397B2_D0004.tif" /></chemistry>

(During the ceremony, X is N or CR¹⁰And Y is N or CH, R¹Is H, or R¹¹And R²Is C₁-C₆Alkyl R³Is H, or R¹¹And R⁴Is C₁-C₄Alkyl or halogen, R⁵Is H, C₁-C₄Alkyl, C₁-C₄Halogen or halogen, R⁷Is C₁-C₄Halogen or halogen, R⁸Is H R⁹Is CF₃, OCF₃, OCHF₂, OCH₂CF₃, S (O)_pCF₃, S (O)_pCHF₂Or halogen, Each R¹¹Independently C₁-C₆Alkylthio; C₁-C₆Haloalkylthio; optionally substituted with 1 to 3 substituents selected independently of W; SN (R)¹⁶)₂; R¹⁴C (= O) L¹-; R¹⁴L²C (= O) S-; R¹⁴L²C (= O) NR¹³S- or R¹⁴SO₂NR¹³S- L¹Is NR¹³Or S Each L²Independently O, NR¹³Or S Each R¹³Independently, hydrogen; optionally halogen, CN, NO, respectively₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino and C₃-C₆C may be substituted with one or more substituents selected from the group consisting of cycloalkylaminos₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne or C₃-C₆Cycloalkyl, Each R¹⁴Halogen, CN, NO, respectively₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino and C₃-C₆C may be substituted with one or more substituents selected from the group consisting of cycloalkylaminos₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne or C₃-C₆Cycloalkyl; or a phenyl optionally substituted with 1 to 3 substituents selected independently of W. R¹⁶Is C₁-C₄Alkyl or C₁-C₄Haloalkyl or N (R¹⁶)₂Can together form a ring that may contain a nitrogen atom, 2-6 carbon atoms and optionally one additional atom of nitrogen, sulfur or oxygen, which ring may optionally. C₁~ C₂Alkyl, halogen, CN, NO₂And C₁-C₂It may be substituted with 1 to 4 substituents selected from the group consisting of alkoxy. However, one R¹¹Exists)

Priority 4. Priority 3 compounds (in the formula, X is N, Y is N, R⁴Is CH₃, F, Cl or Br, R⁵Is H, CF₃, F, Cl, Br or I, R⁷Is Cl or Br, and R⁹Is CF₃, OCHF₂, OCH₂CF₃, Cl or Br. )

Each L²Is O and each R¹³And each R¹⁴Independently C₁-C₆Of note are the preferred 3 and preferred 4 compounds that are alkyl. R¹¹Is R¹⁴L²C (= O) NR¹³Of particular interest are the S-priority 3 and priority 4 compounds.

Priority 5. Priority 2 compound (in the formula, R¹Is H R²Is H or C₁-C₆Alkyl R³Is C₁-C₆Alkyl R⁵Is CN, NO₂, NH₂, Hydroxy and R⁶C substituted with one substituent substituted from the group consisting of₁-C₁₀Alkyl; or R¹²And R⁶Is R¹⁹C (= E)-, R¹⁹C (= E) L-, R¹⁹LC (= E)-or (R¹⁹) LC (= E) L-, R¹²Is NH₂, R¹⁹C (= E)-, R¹⁹C (= E) L-, R¹⁹LC (= E)-or (R¹⁹) LC (= E) L-, Each E is independently O or NOR¹⁵And Each L is independently O or NR¹⁸And Each R¹⁵Is independently H or C₁-C₄Alkyl and Each R¹⁸Are independently H, C₁-C₆Alkyl or C₁-C₆It is haloalkyl. )

Priority 5 compounds (in the formula, R⁵Is R¹²And R¹²Is NH₂, R¹⁹C (= O) L- or (R¹⁹) LC (= O) L-, Each L is independently NR¹⁸And then Each R¹⁸Are independently H, C₁-C₆Alkyl or C₁-C₆It is haloalkyl. ) Is noticed.

Priority 5 compounds (in the formula, R⁵Is a hydroxy-substituted C₁-C₁₀Alkyl, or R¹²And R¹²Is R¹⁹C (= E)-or R¹⁹LC (= O)-and E is O or NOR¹⁵And L is O or NR¹⁸And R¹⁵Is H or C₁-C₄Alkyl and R¹⁸Is H, C₁-C₆Alkyl or C₁-C₆It is haloalkyl. ) Also attracts attention.

Priority 5 notable compounds include compounds 4-[[[1- (3-Chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazol-5-yl] carbonyl] amino] -3-methyl-5-[[(1-methyl) Ethyl) amino] carbonyl] methyl benzoate, N- [4-Acetyl-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H- Pyrazole-5-carboxamide, and N- [4-benzoylamino-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H -Pyrazole-5-carboxamide Is included.

Priority 6. Priority 2 compound (in the formula, R¹Is H R²Is H or C₁-C₆Alkyl R³Is C₁-C₆Alkyl R⁵Is H, C₁-C₄Alkyl, C₁-C₄Halogen or halogen, R⁸Is CN, NO₂, NH₂, Hydroxy and R⁶C substituted with one substituent substituted from the group consisting of₁-C₁₀Alkyl; or R¹²And R⁶Is R¹⁹C (= E)-, R¹⁹C (= E) L-, R¹⁹LC (= E)-or (R¹⁹) LC (= E) L-, R¹²Is R¹⁹C (= E¹)-, R¹⁹C (= E²) L-, R¹⁹LC (= E)¹)-Or (R¹⁹) LC (= E²) L- Each E is independently O or NOR¹⁵And Each E¹Is NOR¹⁵And Each E²Is independently O or NOR¹⁵And Each L is independently O or NR¹⁸And Each R¹⁵Is independently H or C₁-C₄Alkyl Each R¹⁸Are independently H, C₁-C₆Alkyl or C₁-C₆Haloalkyl and Each R¹⁹Are independently H, C₁-C₆Alkyl, C₁-C₆Haloalkyl, C₃-C₆Cycloalkyl, or phenyl optionally substituted with 1 to 3 substituents selected independently of W. )

Priority 6 compounds (in the formula, R⁸Is NH₂, Hydroxy and R⁶C substituted with one substituent substituted from the group consisting of₁-C₁₀Alkyl; or R¹²And R⁶Is R¹⁹C (= O) L-, R¹²Is R¹⁹LC (= O)-and Each L is independently NR¹⁸Is. ) Is noticed.

Notable compounds include 1- [2- (hydroxymethyl) phenyl] -N- (2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl) -3- (trifluoromethyl). -1H-pyrazole-5-carboxamide is included.

Priority 7. Priority 2 compound (in the formula, R¹Is H R²Is H or C₁-C₆Alkyl R³Is one R⁶C replaced by₁-C₆Alkyl R⁴Is C₁-C₄Alkyl or halogen, R⁵Is H, C₁-C₄Alkyl, C₁-C₄Halogen or halogen, R⁶Is R¹⁹C (= E¹)-, R¹⁹C (= E²) L-, R¹⁹LC (= E)¹)-Or (R¹⁹) LC (= E²) L- Each E¹Independently S, NR¹⁵, NOR¹⁵, NN (R¹⁵)₂And Each E²Are independently O, S, NR¹⁵, NOR¹⁵, NN (R¹⁵)₂And Each L is independently O or NR¹⁸And R⁷Is C₁-C₄Halogen or halogen, R⁸Is H R⁹Is CF₃, OCF₃, OCHF₂, OCH₂CF₃, S (O)_pCF₃, S (O)_pCHF₂Or halogen, Each R¹⁵Independently H; C₁-C₆Haloalkyl; possibly CN, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl and C₁-C₄C which may be substituted with one substituent substituted from the group consisting of haloalkylsulfonyls₁-C₆Alkyl Each R¹⁹Is independently H or C₁-C₆Alkyl and Each p is 0, 1 or 2 independently. )

Priority 8. Priority 7 compounds (in the formula, R³Is one R⁶C replaced by₁-C₆Alkyl R⁶Is R¹⁹C (= E¹)-And E¹Is NOR¹⁵Is. )

R⁵Is NH₂Of note are compounds of formula I, including, but not limited to, priority 1, priority 2 and priority 5.

Notable compounds include N- [4-amino-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -1- (3-chloro-2-pyridinyl) -3-( Includes trifluoromethyl) -1H-pyrazol-5-carboxamide.

The present invention is also a method of controlling invertebrate pests, which involves contacting the invertebrate or its environment with a biologically effective amount of a compound of formula I, its N-oxide or a salt thereof. Also related to the method including. Preferred methods include, as preferred, compounds of Formula I of Priority 1-8, and particularly preferred compounds above.

The present invention is also a composition for controlling invertent pests, in biologically effective amounts of compounds of formula I, their N-oxides or salts thereof, and surfactants, solid diluents. Also related to compositions comprising at least one additional component selected from the group consisting of liquid diluents and / or at least one additional biologically active compound or agent in an effective amount. Preferred compositions include, as preferred, compounds of formulas I of preference 1-8, and particularly preferred compounds above.

Expression Ip

<chemistry num="5"><img file="JP4224397B2_D0005.tif" /></chemistry>

(During the ceremony, A and B are independently O or S, X is N or CR¹⁰And Y is N or CH, R¹Is H; or each, in some cases R⁶, Halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino and C₃-C₆Cycloalkylamino or R¹¹May be substituted with one or more substituents selected from the group consisting of C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne or C₃-C₆Cycloalkyl; or R¹¹And R²Is H, C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne, C₃-C₆Cycloalkyl, C₁-C₄Alkoxy, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino, C₂-C₆Alkoxycarbonyl or C₂-C₆Alkylcarbonyl, R³Is H; R¹¹C₁-C₄Alkoxy; C₁-C₄Alkylamino; C₂-C₈Dialkylamino; C₃-C₆Cycloalkylamino; C₂-C₆Alkoxycarbonyl; C₂-C₆Alkylcarbonyl; each, in some cases R⁶, Halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₃-C₆Trialkylsilyl, R¹¹, Or each ring may be substituted with 1 to 3 substituents selected independently of W and optionally 1 R¹²May be substituted with one or more substituents selected from the group consisting of phenyl, phenoxy, or 5- or 6-membered aromatic heterocycles optionally substituted with C.₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne, C₃-C₆Cycloalkyl; or R²And R³Can form K together with the nitrogen they are bound to, R⁴Is C₁-C₄Alkyl, C₁-C₄Haloalkyl, CN, halogen, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄It is a haloalkyl sulfonyl and R⁵And R⁸Are independently H; R¹²; G; J; OJ; OG; S (O)_p-J; S (O)_p-G; In some cases, it may be substituted with 1 to 3 substituents selected independently of W, and in some cases, 1 R.¹²May be replaced by S (O)_p-Phenyl; G, J, R respectively⁶, Halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄Haloalkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylcarbonyl, C₃-C₆Trialkylsilyl, or each ring may optionally be substituted with 1 to 3 substituents selected independently of W and optionally 1 R.¹²C substituted with one or more substituents selected from the group consisting of phenyl or phenoxy rings optionally substituted with₁-C₁₀Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne, C₁-C₄Alkoxy or C₁-C₄Alkylthio Each R⁶Independently, R¹³C (= E)-, R¹⁴C (= E) L-, R¹³LC (= E)-, (R¹⁴) LC (= E) L-, -O (Q =) P (OR)¹⁴)₂, -SO₂LR¹³, Or R¹⁴SO₂L- R⁷Is H, C₁-C₄Alkyl, C₁-C₄Haloalkyl, halogen, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄It is a haloalkyl sulfonyl and R⁹Is CF₃, OCF₃, OCHF₂, S (O)_pCF₃, S (O)_pCHF₂Or halogen, R¹⁰Is H, C₁-C₄Alkyl, C₁-C₄Haloalkyl, halogen, CN or C₁-C₄It is haloalkoxy and Each R¹¹Independently C₁-C₆Alkylthio, C₁-C₆Haloalkylthio, phenylthio, SN (R)¹⁶)₂, R¹³C (= O)-, R¹⁴C (= O) L-, R¹³LC (= O)-or R¹³LC (= O) NR¹³S- Each R¹²Independently, B (OR¹⁷)₂, SH, Thiosianato, C₃-C₈Trialkylsilyloxy, C₁-C₄Alkyl disulfide, SF₅, R¹³C (= E)-, R¹⁴C (= E) L-, R¹³LC (= E)-, (R¹³) LC (= E) L-, -OP (= Q) (OR¹⁴)₂, -SO₂LR¹³, R¹⁴SO₂L- Each E is O, S, NR¹⁵, NOR¹⁵, NN (R¹⁵)₂, NS = O, N-CN or N-NO₂And Each G is independently C (= O), SO or S (O)₂Arbitrarily contains one or two ring elements selected from the group consisting of and optionally C₁-C₂Alkyl, halogen, CN, NO₂And C₁-C₂It is a 5- or 6-membered non-aromatic heterocycle, which may be substituted with 1 to 4 substituents substituted from the group consisting of alkoxy, or Each G is independent, C₃-C₇Cycloalkyl, C₃-C₇Halocycloalkyl, C₃-C₇Cyanocycloalkyl, C₃-C₇Alkylcycloalkyl, C₄-C₈Cycloalkylalkyl, C₄-C₈Halocycloalkylalkyl, Each J may be substituted with 1 to 3 substituents independently selected independently of W and optionally R.¹²A 5- or 6-membered aromatic heterocycle optionally substituted with, Each K is a substituent pair (R)¹³)₂, (R¹⁵)₂Or (R¹⁶)₂Is a ring that may contain 2 to 6 carbon atoms and optionally an additional nitrogen, sulfur or oxygen atom in addition to the nitrogen atom to which the ring is attached, which ring is optionally C.₁-C₂Alkyl, halogen, CN, NO₂And C₁-C₂A ring that may be substituted with 1 to 4 substituents selected from the group consisting of alkoxy. Each L is independently O, NR¹³Or S Q is O or S W is C₁-C₄Alkyl, C₂-C₄Alkenyl, C₂-C₄Alkyne, C₃-C₆Cycloalkyl, C₁-C₄Haloalkyl, C₂-C₄Haloalkenyl, C₂-C₄Halo alkynyl, C₃-C₆Halocycloalkyl, halogen, CN, NO₂, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino, C₃-C₆(Alkyl) Cycloalkylamino, C₂-C₄Alkylcarbonyl, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylaminocarbonyl, C₃-C₈Dialkylaminocarbonyl or C₃-C₆Trialkylsilyl, Each R¹³Independently, hydrogen, C₁-C₆Alkyl or C₁-C₆Haloalkyl or N (R¹³)₂Can form K together, Each R¹⁴Is C₁-C₆Alkyl, C₁-C₆It may be substituted with haloalkyl, or optionally 1 to 3 substituents selected independently of W and optionally R.¹²Phenyl which may be substituted with Each R¹⁵Is independent of hydrogen; C₁-C₆Haloalkyl; possibly CN, NO₂, R⁶, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄Haloalkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylcarbonyl, C₃-C₆It may be substituted with trialkylsilyl, or optionally 1 to 3 substituents selected independently of W, and optionally 1 R.¹²May be substituted with one or more substituents selected from the group consisting of phenyl rings optionally substituted with C₁-C₄Alkyl; or may be substituted with 1 to 3 substituents selected independently of W and optionally R¹²Phenyl which may be substituted with, or N (R¹⁵)₂Can form K together, R¹⁶Is C₁-C₄Alkyl or C₁-C₄Haloalkyl or N (R¹⁶)₂Can form K together, Each R¹⁷Is independently H or C₁-C₄Alkyl or B (OR¹⁷)₂Is that the two oxygen atoms are methyl or C in some cases₂-C₆It is possible to form a ring linked by a chain of 2-3 carbons, which may be substituted with 1 or 2 substituents independently selected from the alkoxycarbonyl, and p is 0, 1 or 2, However, (a) R⁵Is H, C₁-C₆Alkyl, C₁-C₆Haloalkyl, C₂-C₆Haloalkenyl, C₂-C₆Halo alkynyl, C₁-C₄Haloalkoxy, C₁-C₄Haloalkylthio or halogen and (b) R⁸Is H, C₁-C₆Alkyl, C₁-C₆Haloalkyl, C₂-C₆Haloalkenyl, C₂-C₆Halo alkynyl, C₁-C₄Haloalkoxy, C₁-C₄Haloalkylthio, halogen, C₂-C₄Alkylcarbonyl, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylaminocarbonyl or C₃-C₈In the case of dialkylaminocarbonyl, (c) R⁶, R¹¹And R¹²There is at least one substituent selected from the group consisting of, and (d) R¹²At least one R if does not exist⁶Or R¹¹Is C₂-C₆Alkylcarbonyl, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylaminocarbonyl and C₃-C₈Other than dialkylaminocarbonyl. ) Of note are the compounds of the above, their N-oxides and agriculturally suitable salts.

R⁶And R¹²Of particular interest are compounds of formula Ip that have at least one group selected from. At least one R¹¹Of particular interest are compounds of formula Ip in which.

As mentioned above, some kind of R¹, R³, R⁵, R⁸, R¹³, R¹⁴, R¹⁵And R¹⁹The groups can be optionally substituted with one or more substituents. These R^vThe term "possibly substituted" in relation to a group (where v is 1, 3, 5, 8, 13, 14, 15 or 19) is unsubstituted or at least one. R with non-hydrogen substituents^vRelated to the group. R which may be replaced in some cases^vExamples of groups are one or more selected independently of the substituents listed in "Means to Solve the Problem" above (any specific R).^vR at the substituent (up to the total number of hydrogens available for substitution at the group)^vIt is arbitrarily substituted by the substitution of hydrogen on the carbon atom of the group. Although these substituents are listed, it is specifically mentioned that they do not need to be present as they are arbitrary substituents. Non-replacement R^vAttention is paid to the group. R substituted with 1-5 substituents^vAttention is paid to the group. Also, R substituted with one substituent^vThe group is also noticed.

As mentioned above, each J may be independently substituted with 1 to 3 substituents selected independently of W and optionally R.¹²A 5- or 6-membered aromatic heterocycle that may be substituted with. The term "optionally substituted" in connection with these J groups relates to groups that are unsubstituted or have at least one non-hydrogen substituent. Examples of 5- or 6-membered aromatic heterocycles include rings U-1 to U-48 illustrated in Exhibit 1. Each of the U-rings may be substituted with 1 to 3 substituents selected independently of W and optionally R¹²Can be optionally replaced with (the W and R)¹²Note that the group is not exemplified in Exhibit 1 as it is an arbitrary substituent). Note that J-1 to J-4 above also show a 5- or 6-membered aromatic heterocycle. U-1 to U-19 are examples of J-1, U-20 to U-35 are examples of J-2, U-36 to U-43 are examples of J-3, and U Note that -44 to U-48 are examples of J-4. Nitrogen atoms that require substitution to satisfy their valence are substituted with H or W. Some U groups have less than 3 Ws and / or 1 R¹²It can only be replaced by a group (for example, U-12, U-14, U-17 to U-20, U-31 to U-33 and U-35 can only be replaced by one group). Please be careful.

<chemistry num="6"><img file="JP4224397B2_D0006.tif" /></chemistry>

<chemistry num="7"><img file="JP4224397B2_D0007.tif" /></chemistry>

As mentioned above, each G is independently C (= O), SO or S (O)₂Arbitrarily contains one or two ring elements substituted from the group consisting of, and optionally C₁-C₂Alkyl, halogen, CN, NO₂And C₁-C₂A 5- or 6-membered non-aromatic heterocyclic ring that may be substituted with 1 to 4 substituents selected from the group consisting of alkoxy. The term "optionally substituted" in connection with these G groups relates to groups that are unsubstituted or have 1 to 4 non-hydrogen substituents. Examples of such G groups include those exemplified as G-1 to G-35 in Exhibition 2. Note that if the bond points on these G groups are exemplified as floating, the G group can be attached to the rest of formula I through any available carbon or nitrogen of the G group by substitution of a hydrogen atom. I want to. Any substituent can be attached to any available carbon or nitrogen by substituting a hydrogen atom (the substituent is an arbitrary substituent and is not exemplified in Exhibit 2). If G contains a ring selected from G-24 to G-31, G-34 and G-35, then Q²Is O, S, NH or N (C₁-C₂Note that it is selected from (alkyl).

<chemistry num="8"><img file="JP4224397B2_D0008.tif" /></chemistry>

One or more of the following methods and variations as described in Scheme 1-29 can be used to make compounds of formula I. A, B, G, J, R in the compounds of formula 2-67 below¹From R⁷, M, n and p are as defined above. The compounds of formulas Ia-f, 2a-b, 4a-k, 5a-b are various subsets of the compounds of formulas I, 2, 4 and 5. In the scheme, Het is the part shown below.

<chemistry num="9"><img file="JP4224397B2_D0009.tif" /></chemistry>

In the formula, the wavy line indicates the bond that connects the moiety to the rest of the formula for a given compound.

A typical procedure for the preparation of formula I is detailed in Scheme 1 with the amine of formula 2 and the acid chloride of formula 3 in the presence of an acid scavenger to give the compound of formula Ia. Accompanied by the coupling of. Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine, while other acid scavengers include sodium hydroxide and potassium and carbonates such as sodium carbonate and potassium carbonate. Is done. In certain cases, polymer-bearing acid scavengers such as polymer-linked diisopropylethylamine and polymer-linked dimethylaminopyridine may be used. The coupling can be carried out in a suitable inert solvent such as tetrahydrofuran, dioxane, diethyl ether or dichloromethane to give the anilide of formula Ia. In the next step, the amide of formula Ia can be converted to the thioamide of formula Ib using a variety of standard thiotranslocation reagents, including phosphorus pentasulfide and Lawesson's reagents.

<chemistry num="10"><img file="JP4224397B2_D0010.tif" /></chemistry>

Alternative procedures for producing compounds of formula Ia are dicyclohexylcarbodiimide (DCC), 1,1'-carbonyldiimidazole, bis (2-oxo-3-oxazolidinyl) phosphinated or benzotriazole-1-yloxytris. With the coupling of the amine of formula 2 with the acid of formula 4 in the presence of a dehydrating agent such as (dimethylamino) -phosphonium hexafluorophosphate. Polymer-supporting reagents such as polymer-bound cyclohexylcarbodiimides are also useful here. The coupling can be carried out in a suitable inert solvent such as dichloromethane or N, N-dimethylformamide. Since the synthetic literature is extensive for this type of reaction, the synthetic procedures of Schemes 1 and 2 are only representative examples of useful methods for the preparation of Formula I compounds.

<chemistry num="11"><img file="JP4224397B2_D0011.tif" /></chemistry>

Those skilled in the art will also appreciate that the acid chloride of formula 3 may be prepared from the acid of formula 4 by a number of well-known methods. For example, the acid chloride of formula 3 is prepared by reacting carboxylic acid 4 with thionyl chloride or oxalyl chloride in the presence of a catalytic amount of N, N-dimethylformamide in an inert solvent such as toluene or dichloromethane. Easily made from the carboxylic acid of.

The amine of formula 2a is typically available from the corresponding 2-nitrobenzamide of formula 5 by catalytic hydrogenation of the nitro group (Scheme 3). A typical procedure involves reduction with hydrogen in a hydroxyl group-containing solvent such as ethanol and isopropanol in the presence of a metal catalyst such as palladium-carbon or platinum oxide. They can also be produced by reduction with zinc in acetic acid. These methods for reducing nitro groups are well documented in the chemical literature. R like alkyl, substituted alkyl, etc.¹Substituents can generally be introduced at this stage by known procedures, including either direct alkylation of amines or generally preferred methods of reduction alkylation. A commonly used procedure is to combine amine 2a with an aldehyde in the presence of a reducing agent such as sodium cyanoborohydride.¹Is to produce a compound of formula 2b which is an alkyl, alkenyl, alkynyl or a substituted derivative thereof.

<chemistry num="12"><img file="JP4224397B2_D0012.tif" /></chemistry>

Scheme 4 is suitable for compounds of formula Ic such as alkyl halides in the presence of bases such as sodium hydride or n-butyllithium in inert solvents such as tetrahydrofuran or N, N-dimethylformamide. Alkylated with an alkylating agent, R¹Shows that can give an anilide of formula Id other than hydrogen. This procedure is R¹Is particularly useful for making compounds of formula Id where is alkyl, alkenyl or alkynyl.

<chemistry num="13"><img file="JP4224397B2_D0013.tif" /></chemistry>

The intermediate amide of formula 5a is readily prepared from commercially available 2-nitrobenzoic acid (Scheme 5). Typical methods for amide formation can be applied here. These include the direct dehydration coupling of the acid of formula 6 with the amine of formula 7 using DCC and the conversion of the acid to an activated form such as an acid chloride or acid anhydride and the formation of an amide of formula 5a. Coupling with the following amines is included. Alkyl chloroformate, such as ethyl chloroformate or isopropyl chloroformate, is a particularly useful reagent for this type of reaction involving acid activation. The chemical literature is extensive on this type of amide formation. The amide of formula 5a is readily converted to the thioamide of formula 5b by using commercially available thiotranslocation reagents such as phosphorus pentasulfide and Lawesson's reagent.

<chemistry num="14"><img file="JP4224397B2_D0014.tif" /></chemistry>

The intermediate anthranilamides of formulas 2c and 2d may also be prepared from the isatonic anhydrides of formulas 8 and 9 (Scheme 6). A typical procedure is to combine equimolar amounts of amine 7 with isatoic anhydride in polar aprotic solvents such as pyridine and N, N-dimethylformamide at temperatures ranging from room temperature to 100 ° C. Accompany. R like alkyl and substituted alkyl¹Substituents are known alkylating agents R¹Introduced by base-catalyzed alkylation of isatoic anhydride with -Lg (where Lg is a leaving group such as halogen, alkyl or aryl sulfonate or alkyl sulphate), even given an alkyl-substituted intermediate 9. Good. The isatoic anhydride of formula 8 may be prepared by the method described in Coppola, Synthesis, 1980, pp. 505-36.

<chemistry num="15"><img file="JP4224397B2_D0015.tif" /></chemistry>

As shown in Scheme 7, an alternative procedure for producing a particular compound of formula Ic involves the reaction of amine 7 with benzoxazinone of formula 10. A typical procedure involves the combination of amine and benzoxazinone in a solvent such as tetrahydrofuran or pyridine at temperatures ranging from room temperature to solvent reflux temperature. Benzoxazinone is well documented in the chemical literature and is available by known methods involving coupling of either anthranilic acid or isatonic anhydride with the acid chloride. For the synthesis and chemistry of benzooxadinone, see Jakobsen et al., Biorganic and Medical Chemistry, 2000, 8, pp. 2095-2103 and the references cited therein. See also Coppola, J. Heterocyclic Chemistry, 1999, 36, pp. 563-588.

<chemistry num="16"><img file="JP4224397B2_D0016.tif" /></chemistry>

A preferred set of compounds of formula Ic is R³The substituent contains an oxime group. Amines of formula 7 containing oxime side chains are known (see, eg, US Pat. No. 5,211,738 and European Patent Application EP117,477). The benzoxazineone root of Scheme 7 is R³This is the preferred method for the production of compounds of formula Ic containing an oxime group in the substituent.

Scheme 8-11 depicts the typical acid synthesis of Equation 4. Scheme 8 illustrates the synthesis of pyrazole of formula 4a. The synthesis of the compound of formula 4a in Scheme 8 involves the introduction of a phenyl or pyridinyl substituent by arylation of pyrazole in the compound of formula 12 as a key step. Oxidation of the methyl group gives pyrazole carboxylic acid. More preferred R⁹Some of the groups include haloalkyl.

<chemistry num="17"><img file="JP4224397B2_D0017.tif" /></chemistry>

Scheme 9 illustrates the synthesis of pyrazole and pyrrole of formula 4b. These acids may be produced by metallization and carboxylation of the compounds of formula 15 as a key step. The phenyl or pyridinyl group is introduced in a manner similar to that of Scheme 7, i.e. by arylation with the compound of formula 12. Typical R⁹Groups include, for example, cyano, haloalkyl and halogens.

<chemistry num="18"><img file="JP4224397B2_D0018.tif" /></chemistry>

Scheme 10 illustrates the synthesis of pyrazole of formula 4c. They can be prepared by the reaction of hydrazine, which may be optionally substituted in the case of formula 16, with the pyruvate ester of formula 17 to give the pyrazole ester of formula 18. Hydrolysis of the ester gives the pyrazole acid of formula 4c. This procedure is for phenyl, where the substituents may optionally be substituted, R⁹Is particularly useful for the production of compounds in which is haloalkyl.

<chemistry num="19"><img file="JP4224397B2_D0019.tif" /></chemistry>

Scheme 11 illustrates the synthesis of pyrazole acid of formula 4d. They can be prepared by 3 + 2 cycloaddition of appropriately substituted nitrile imines with either the substituted propiolic acid ester of formula 20 or the acrylic acid ester of formula 23. Cycloaddition with an acrylic acid ester requires additional oxidation of the intermediate pyrazoline to pyrazole. Hydrolysis of the ester gives the pyrazole acid of formula 4d. Preferred iminohalides for this reaction include trifluoromethyliminochloride of formula 25 and iminodibromid of formula 26. Compounds such as 25 are known (J. Heterocycl. Chem. 1985, 22 (2), pp. 565-8). Compounds such as 26 are available by known methods (Tetrahedron Letters 1999, 40, 2605). These procedures are for phenyls where the substituents may optionally be substituted (X is CR).¹⁰Is), R⁹Is particularly useful for the production of compounds in which is haloalkyl or bromo.

<chemistry num="20"><img file="JP4224397B2_D0020.tif" /></chemistry>

Scheme 12 shows the synthesis of pyrazole acid of structure 4e.

<chemistry num="21"><img file="JP4224397B2_D0021.tif" /></chemistry>

The compound of formula 27 is formylated with a formylating agent such as N, N-dimethylformamide combined with an activator such as phosphorus oxychloride, thionyl chloride, or oxalyl chloride to give the aldehyde of formula 28. You may. Halogenation of a compound of formula 28 with a molecular halogen or N-halosuccinimide yields a compound of formula 29. Oxidation of the aldehyde group with various known reagents such as silver oxide, alkali dichromate, or alkali chlorate gives the acid of formula 4e.

R in the formula, as shown in Scheme 13¹Or R³Compounds of formula If, where either is alkylcarbonyl, alkoxycarbonyl, or fluphenyl, may be prepared by treatment of the compound of formula Ie with an activated chloride of formula 30 in the presence of an acid acceptor.

<chemistry num="22"><img file="JP4224397B2_D0022.tif" /></chemistry>

The compound of formula 30 in which V is an alkylcarbonyl in the formula is well known in the art and corresponds to the corresponding carboxylic acid in an inert solvent such as toluene or dichloromethane in the presence of a catalytic amount of N, N-dimethylformamide. It can generally be produced by reaction of the acid with a chlorinating agent such as thionyl chloride or oxalyl chloride. The compound of formula 30 in which V is alkoxycarbonyl in the formula is well known in the art and can generally be prepared by the reaction of an alcohol with a phosgene.

The compound of formula 30 in which V is sulfenyl in the formula can be prepared by the method described on Kuehle, Synthesis, 1970, 561. N-chlorosulfenyl carbamate, V in the formula is R¹³OC (= O) NR¹³S (O)_n-The compound of formula 30 which is can be prepared according to the procedure of US Pat. No. 3,843,689. Other halogenated sulphenyls have been produced in the same manner (see US Pat. No. 3,843,689 and European Patent Application EP395581). These references also describe N-sulfenylation of amides and other analogs by reaction with sulphenyl halides in the presence of bases.

As shown in Scheme 13a, the sulfenyl compound of formula Ig, i.e. R in the formula.¹Or R³R bonded through a sulfur atom¹¹Compounds (eg, in the formula, R¹¹Is C₁-C₆Alkylthio; C₁-C₆Haloalkylthio; optionally substituted with 1 to 3 substituents selected independently of W; (R)¹⁶)₂NS (O)_n-; R¹⁴C (= O) L-; R¹³LC (= O) S-; R¹³C (= O) NR¹³S (O)_n-; R¹³LC (= O) NR¹³S (O)_n-Or R¹³LSO₂NR¹³S (O)_n-And n is 0) are organic peroxides, including peracids such as hydrogen peroxide, perbenzoic acid or peracetic acid, potassium persulfate, sodium persulfate, ammonium persulfate or mono. Compounds of formula Ih (eg, in formula, R) by treatment with potassium persulfate (eg, Oxone®).¹¹Is C₁-C₆Alkyl sulphenyl; C₁-C₆Haloalkyl sulphenyl; Phenyl sul phenyl optionally substituted with 1 to 3 substituents selected independently of W; (R)¹⁶)₂NS (O)_n-; R¹⁴C (= O) L-; R¹³LC (= O) S-; R¹³C (= O) NR¹³S (O)_n-; R¹³LC (= O) NR¹³S (O)_n-Or R¹³LSO₂NR¹³S (O)_n-And can be oxidized to (n is 1).

<chemistry num="23"><img file="JP4224397B2_D0023.tif" /></chemistry>

As shown in Scheme 14, the compound of formula 33 (where R¹²Contains a nitrogen atom bonded to the benzene ring) can be prepared via the nitro-substituted compound of formula 31. Reduction of nitro compounds is a well-known process and can be carried out by a number of different methods, such as by catalytic hydrogenation, iron-acetic acid reduction, zinc-trifluoroacetic acid reduction or tin (II) chloride reduction (). For various methods of nitro group reduction, see "Comprehensive Organic" by Larock. See Transformations, pp. 411-415, 1989, VCH, New York). Catalytic reduction with a palladium or platinum catalyst in a hydrogen atmosphere is the preferred method for carrying out this conversion. Acylation or sulfonylation of the intermediate of formula 32 in the presence of an acid receptor yields the compound of formula 33. Preferred acid receptors are alkali carbonates, alkali hydroxides, and tertiary amines. Suitable reagents for acylation or sulfonylation in this route include acid anhydrides, acid chlorides, sulfonyl halides, isocyanates, chloroformates, and carbamyl chloride. Preferred solvents include dichloromethane, tetrahydrofuran, N, N-dimethylformamide, acetonitrile, and ethyl acetate. Acylation and sulfonylation of amines are well known in the art.

<chemistry num="24"><img file="JP4224397B2_D0024.tif" /></chemistry>

As shown in Scheme 15, compounds of formulas 35, 36, and 37 containing esters, amides, and ketones, respectively, may be prepared by carbonylation of the halides and sulfonates of formula 34. Palladium-catalyzed reactions of aromatic halides and sulfonates in the presence of carbon monoxide and nucleophiles are well known in the art. Suitable nucleophiles include alcohols, amines, boronic acids, and organotins. To synthesize ester 35 or amide 36, the compound of formula 34 is in the presence of a palladium catalyst and a phosphine ligand in an aprotic solvent such as dimethyl sulfoxide, N, N-dimethylformamide or N-methylpyrrolidinone. Treated with alcohol or amine in an atmosphere of carbon monoxide. The reaction can be carried out at 25-120 ° C. Preferred catalytic systems arise from palladium acetate and diphenylphosphinopropane. Leading references to the transformation are Tetrahedron. Found in Letters, 1992, 33, 1959-1962. Organic tin or organoboron compounds may be used in the reaction to produce the ketone of formula 37 as a product. For procedures and conditions for the conversion of halides and sulfonates to ketones, Synthesis, 1992, pp. 803-815, Angewandte Chemie Int. Ed., 1986, 25, 508-524 and J. Org. Chem., 1998, 63. , See page 4726 and references within them. Additional methods for the conversion of halides and sulfonates to methylketones that do not require carbon monoxide are disclosed in Bull. Chem. Soc. Japan, 1987, 60, 767-8.

<chemistry num="25"><img file="JP4224397B2_D0025.tif" /></chemistry>

Scheme 16 shows the conversion of a compound of formula 34 to a compound of formula 38, in which the substituent is either G or J depending on the organometallic reagent used. The introduction of complex aromatic groups by transition metal-catalyzed cross-coupling reactions is well known in the art. Various heterocyclic organometallic reagents (such as zinc, boron and tin reagents) will couple with halides and sulfonates of formula 34. Suitable specific conditions for the conversion of halides and sulfonates to complex aromatic groups are Synthesis, 1992, pp. 413-432 and Advances in Heterocyclic. It can be found in Chemistry, 1995, 62, pp. 305-418. Synthesis of many complex aromatic reagents suitable for coupling is found in these references as well. In general, the reaction requires the use of a palladium or nickel catalyst, a halide or sulfonate of formula 34, and a heterocyclic organometallic reagent (G-metal or J-metal). Suitable solvents include N, N-dimethylformamide, N-methylpyrrolidinone, tetrahydrofuran, dioxane, and other solvents that do not react with organometallic reagents. In the case of boronic acid, the presence of an alkaline carbonate base and a mixed aqueous and organic solvent is preferred. Reaction temperatures between 0 ° C and 120 ° C are preferred. Preferred catalysts are Pd (PPh)₃)₂Cl₂And Pd (PPh)₃)₄Is included.

<chemistry num="26"><img file="JP4224397B2_D0026.tif" /></chemistry>

Isatin of formula 40 can be prepared by demethylation of the methoxy-substituted compound of formula 39 in scheme 17. Further alkylation, acylation, phosphorylation and sulfonylation with appropriate halides in the presence of acid receptors can be performed with isatin of formula 41 (in formula, R).⁵Is OJ; OG; or G, J, R⁶, Halogen, CN, NO₂, NH₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄C substituted with one or more substituents selected from the group consisting of haloalkoxy₁-C₄Those Rs bonded to the ring by O, such as alkoxy⁵Represents a substituent). For demethylation of methyl ethers, see Brooks et al., J. Org. Chem., 1999, 64, 9719-9721 and references therein for the different reagents and conditions for performing this conversion. I want to be. Many reagents are useful for this conversion, but the preferred method is to use boron tribromide in dichloromethane. The conversion can be carried out at temperatures between -70 ° C and 110 ° C ° C. For functionalization of the phenolic product of formula 40 by alkylation, acylation, phosphorylation and sulfonylation with appropriate halides, preferred acid acceptors are alkali carbonates, alkali hydroxides, and tertiary amines. Preferred solvents include dichloromethane, tetrahydrofuran, N-methylpyrrolidinone, N, N-dimethylformamide, acetonitrile, and ethyl acetate. The use of demethylation and alkylation procedures may also be carried out at the final product stage of anthranilic acid or synthesis.

<chemistry num="27"><img file="JP4224397B2_D0027.tif" /></chemistry>

Nucleophilic substitution of halonitrocarboxamide of formula 42 is shown for giving the compound of formula 43 to scheme 18. Reactions of compounds of formula 42 with nucleophiles such as alkoxides and thiolates lead to compounds of formula 43. Suitable solvents include, but are not limited to, N, N-dimethylformamide, N-methylpyrrolidinone, dimethyl sulfoxide, tetrahydrofuran, and dioxane. The replacement can be carried out at a temperature of 0 to 160 ° C. This method is R⁵Like OJ, OG, SJ, SG, cycloalkoxy, alkenyloxy, alkynyloxy, substituents selected from optionally substituted alkoxy and optionally substituted alkylthio substituents (but R attached to the aromatic ring by O or S (but not limited to them)⁵It is suitable for synthesizing the compound of formula 43 representing a substituent.

<chemistry num="28"><img file="JP4224397B2_D0028.tif" /></chemistry>

As shown in Scheme 18a, the sulfenyl compound of formula 43a, ie, in the formula, R⁵Compounds attached to the aromatic ring by S (but not limited to) such as, but not limited to, SJ, SG and optionally substituted phenylthio substituents are hydrogen peroxide, perbenzoic acid or persulfates. Compounds of formula 44 by treatment with organic peroxides, including peracids such as acetic acid, potassium persulfate, sodium persulfate, ammonium persulfate or potassium monosulfate (eg, Oxon®). (For example, in the formula, R⁵Is S (O)_p-J; S (O)_p-G; S (O)_p-Can be oxidized to (Phenyl which may be substituted in some cases) and p is 1 or 2). One equivalent (for p is 1) or two equivalents (for p is 2) of oxidizer is used.

<chemistry num="29"><img file="JP4224397B2_D0029.tif" /></chemistry>

R in the formula⁹Is CF₃The pyrazole carboxylic acid of formula 4f, which is, can be prepared by the method outlined in Scheme 19.

<chemistry num="30"><img file="JP4224397B2_D0030.tif" /></chemistry>

In a suitable organic solvent, R in the formula²⁰Is C₁-C₄Reaction of a compound of formula 45, which is alkyl, with a suitable base gives the cyclization product of formula 46 after neutralization with an acid such as acetic acid. Suitable bases are, for example, sodium hydride, potassium t-butoxide, sodium gymsyl (CH).₃S (O) CH₂^-Na⁺, Alkali metals (such as lithium, sodium or potassium) carbonates or hydroxides, fluoride or tetraalkyl hydroxides (such as methyl, ethyl or butyl) ammonium, or 2-tertiary butylimino-2-diethylamino- It can be, but is not limited to, 1,3-dimethyl-perhydro-1,3,2-diazaphosphonin. Suitable organic solvents can be, but are not limited to, for example, acetone, acetonitrile, tetrahydrofuran, dichloromethane, dimethyl sulfoxide, or N, N-dimethylformamide. The cyclization reaction is usually carried out at temperatures in the range of about 0-120 ° C. The effects of solvent, base, temperature and addition time are all interdependent and the choice of reaction conditions is important to minimize the formation of by-products. A preferred base is tetrabutylammonium fluoride.

Dehydrating the compound of formula 46 to give the compound of formula 47 and subsequently converting the carboxylic acid ester functional group to a carboxylic acid yields the compound of formula 4f. Dehydration is achieved by treatment with a catalytic amount of a suitable acid. The catalytic acid can be, for example, sulfuric acid, but is not limited thereto. The reaction is generally carried out using an organic solvent. As those skilled in the art will appreciate, dehydration reactions occur in a wide variety of solvents, generally at temperatures between about 0 ° C and 200 ° C, more preferably between about 0 ° C and 100 ° C. It may be carried out in a range. For dehydration by the method of Scheme 19, a solvent containing acetic acid and a temperature of about 65 ° C. are preferred. Carboxylic acid ester compounds can be converted to carboxylic acid compounds by a number of methods, including nucleophilic cleavage under anhydrous conditions or hydrolysis methods involving the use of either acids or bases (of the method). For a review, see Protective Groups in Organic Synthesis, 2nd Edition, John Wiley, by TW Greene and PGMWuts. &amp; Sons, New York, 1991, pp. 224-269). As for the method of scheme 19, the base-catalyzed hydrolysis method is preferable. Suitable bases include alkali metal hydroxides (such as lithium, sodium or potassium). For example, ester 47 can be dissolved in a mixture of water and an alcohol such as ethanol. When treated with sodium hydroxide or potassium hydroxide, the ester is saponified to give the sodium or potassium salt of the carboxylic acid. Acidification with a strong acid such as hydrochloric acid or sulfuric acid results in the carboxylic acid of formula 4f. Carboxylic acids can be isolated by methods known to those of skill in the art, including crystallization, extraction and distillation.

The compound of formula 45 can be prepared by the method outlined in Scheme 20.

<chemistry num="31"><img file="JP4224397B2_D0031.tif" /></chemistry>

In the formula, R⁹Is CF₃And R²⁰Is C₁-C₄It is alkyl.

Treatment of a hydrazine compound of formula 48 with a ketone of formula 49 in a solvent such as water, methanol or acetic acid yields a hydrazone of formula 50. Those skilled in the art will appreciate that this reaction requires catalysis with any acid and may also require high temperatures depending on the molecular substitution pattern of the hydrazone of formula 50. The reaction of a hydrazone of formula 50 with a compound of formula 51 in the presence of an acid scavenger such as triethylamine in a suitable organic solvent such as, but not limited to, dichloromethane or tetrahydrofuran is a compound of formula 45. give. The reaction is usually carried out at temperatures between about 0 ° C and 100 ° C. The hydrazine compound of formula 48 can be prepared by standard methods, such as by contacting the corresponding halo compound of formula 12 (Scheme 9) with hydrazine.

R in the formula⁹The pyrazole carboxylic acid of formula 4 g of Cl or Br can be prepared by the method outlined in Scheme 21.

<chemistry num="32"><img file="JP4224397B2_D0032.tif" /></chemistry>

In the formula, R²⁰Is C₁-C₄It is alkyl.

Arbitrarily oxidizing the compound of formula 52 in the presence of an acid to give the compound of formula 53 and subsequently converting the carboxylic acid ester functional group to a carboxylic acid yields the compound of formula 4 g. The oxidant can be hydrogen peroxide, an organic peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, potassium monosulfate (eg, Oxone®) or potassium permanganate. To obtain complete conversion, at least 1 equivalent, preferably about 1-2 equivalents of oxidant should be used relative to the compound of formula 52. This oxidation is typically carried out in the presence of a solvent. The solvent can be an ether such as tetrahydrofuran, p-dioxane or the like, an organic ester such as ethyl acetate, dimethyl carbonate or the like, or a polar aprotic organic compound such as N, N-dimethylformamide, acetonitrile or the like. Acids suitable for use in the oxidation step include inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as acetic acid and benzoic acid. When used, the acid should be used in excess of 0.1 equivalents for the compound of formula 52. 1-5 equivalents of acid can be used to obtain complete conversion. The preferred oxidizing agent is potassium persulfate, and the oxidation is preferably carried out in the presence of sulfuric acid. The reaction can be carried out by mixing the compound of formula 52 in a desired solvent and, if used, an acid. The oxidant can then be added at a convenient rate. The reaction temperature varies from as low as about 0 ° C to the boiling point of the solvent to obtain a reasonable reaction time, preferably less than 8 hours, to complete the reaction. The desired product (compound of Formula 53) can be isolated by methods known to those of skill in the art, including crystallization, extraction and distillation. A suitable method for converting an ester of formula 53 to a carboxylic acid of formula 4 g has already been described for scheme 19.

As shown in Scheme 22, the compound of formula 52 can be prepared from the corresponding compound of formula 54.

<chemistry num="33"><img file="JP4224397B2_D0033.tif" /></chemistry>

In the formula, R²⁰Is C₁-C₄It is alkyl.

Treatment of the compound of formula 54 with a halogenating agent, usually in the presence of a solvent, yields the corresponding halo compound of formula 52. Halogenizing agents that can be used include phosphorus oxyhalides, phosphorus trihalogenates, phosphorus pentahalogenates, thionyl chloride, dihalotrialkylphosphorans, dihalodiphenylphosphorans, oxalyl chlorides and phosgenes. Phosphorus oxyhalides and phosphorus pentahalides are preferred. To obtain complete conversion, at least 0.33 equivalents, preferably between about 0.33 equivalents and 1.2 equivalents of phosphorus oxyhalide should be used for the compound of formula 54. To obtain complete conversion, at least 0.20 equivalents, preferably between about 0.20 equivalents and 1.0 equivalents of phosphorus pentahalide should be used for the compound of formula 54. R in the formula²⁰Is C₁-C₄Formula that is alkyl<u style="single">54</u>Compounds are preferred for this reaction. Typical solvents for this halogenation include halogenated alkanes such as dichloromethane, chloroform, chlorobutane and the like, aromatic solvents such as benzene, xylene, chlorobenzene and the like, and ethers such as tetrahydrofuran, p-dioxane, diethyl ether and the like. , And polar aproton solvents such as acetonitrile, N, N-dimethylformamide and the like. Optionally, an organic base such as triethylamine, pyridine, N, N-dimethylaniline, etc. can be added. Addition of catalysts such as N, N-dimethylformamide is also an option. A method in which the solvent is acetonitrile and no base is present is preferable. Typically, no base or catalyst is required when an acetonitrile solvent is used. A preferred method is carried out by mixing the compounds of formula 54 in acetonitrile. The halogenating agent is then added over a convenient time and then the mixture is kept at the desired temperature until the reaction is complete. The reaction temperature is typically between 20 ° C and the boiling point of acetonitrile, and the reaction time is typically less than 2 hours. The reaction mass is then neutralized with an inorganic base such as sodium bicarbonate, sodium hydroxide or the like, or an organic base such as sodium acetate. The desired product (compound of formula 52) can be isolated by methods known to those of skill in the art, including crystallization, extraction and distillation.

Alternatively, R in the formula⁹The compound of formula 52 in which is Br or Cl is R in the formula.⁹Halogen with different (eg, R in equation)⁹To produce Formula 52 in which is Br, the corresponding compounds of Formula 52, which are sulfonate groups such as Cl) or p-toluenesulfonate, are prepared by treatment with hydrogen bromide or hydrogen chloride, respectively. Can be done. By this method, the starting compound R of formula 52⁹Halogen or sulfonate substituents are substituted with Br or Cl from hydrogen bromide or hydrogen chloride, respectively. The reaction is carried out in a suitable solvent such as dibromomethane, dichloromethane or acetonitrile. The reaction can be carried out at about atmospheric pressure or above atmospheric pressure in the pressure vessel. R of the starting compound of formula 52⁹When is a halogen such as Cl, the reaction is preferably carried out in such a way that the hydrogen halide resulting from the reaction is removed by sparging or other suitable means. The reaction should be carried out between about 0 ° C and 100 ° C, most conveniently near ambient temperature (eg, about 10-40 ° C), more preferably between about 20 ° C and 30 ° C. Can be done. Lewis acid catalyst (R in formula)⁹Addition of (such as aluminum bromide) to produce formula 52 in which is Br can accelerate the reaction. The product of formula 52 is isolated by methods known to those of skill in the art, including extraction, distillation and crystallization.

R in the formula⁹The starting compound of formula 52 of which is Cl or Br can be prepared from the corresponding compound of formula 54 as previously described. R in the formula⁹The starting compound of formula 52, which is a sulfonate group, is treated with a base such as sulfonyl chloride (eg, p-toluenesulfonyl chloride) and a tertiary amine (eg, triethylamine) in a suitable solvent such as dichloromethane. It can also be prepared from the corresponding compound of formula 54 by such a standard method.

R in the formula⁹Is OCH₂CF₃Equation 4h or R in equation⁹Is OCHF₂The pyrazole carboxylic acid of formula 4i is can be prepared by the method outlined in Scheme 23. In this method, the compound of formula 54 is oxidized to the compound of formula 55 instead of being halogenated as shown in scheme 22. The reaction conditions for this oxidation are as described above for the conversion of the compound of formula 52 to the compound of formula 53 in scheme 21.

Next, the compound of formula 55 is an alkylating agent CF in the presence of a base.₃CH₂Alkylated by contact with Lg (56), the compound of formula 57 (R)⁹Is OCH₂CF₃Is). In the alkylating agent 56, Lg is halogen (eg Br, I), OS (O).₂CH₃(Methane sulfonate), OS (O)₂CF₃, OS (O)₂Ph-p-CH₃It is a nucleophilic reaction leaving group such as (p-toluenesulfonate), and methanesulfonate works well. The reaction is carried out in the presence of at least 1 equivalent of base. Suitable bases include alkali metal (such as lithium, sodium or potassium) carbonates and hydroxides, as well as triethylamine, diisopropylethylamine and 1,8-diaza-bicyclo- [5.4.0] unde-7-sen. Such organic bases are included. Reactions are generally such as alcohols such as methanol and ethanol, alkane halides such as dichloromethane, aromatic solvents such as benzene, toluene and chlorobenzene, ethers such as tetrahydrofuran, and acetonitrile, N, N-dimethylformamide and the like. It is carried out in a solvent which may contain a protic solvent of various polarities. Alcohols and polar aprotic solvents are preferred for use with inorganic bases. Potassium carbonate is preferred as the base and acetonitrile is preferred as the solvent. The reaction is generally carried out between about 0 ° C and 150 ° C, most typically between ambient temperature and 100 ° C.

<chemistry num="34"><img file="JP4224397B2_D0034.tif" /></chemistry>

In the formula, R²⁰Is C₁-C₄It is alkyl and Lg is a leaving group.

The compound of formula 55 is also CHClF in the presence of a base.₂Alkylated by contact with difluorocarbene produced from the compound of formula 58 (R).⁹Is OCHF₂Can be formed. The reaction is generally carried out in a solvent that may include ethers such as tetrahydrofuran or dioxane and polar aprotic solvents such as acetonitrile, N, N-dimethylformamide and the like. The base can be selected from inorganic bases such as potassium carbonate, sodium hydroxide or sodium hydride. Preferably, the reaction is carried out with potassium carbonate with N, N-dimethylformamide as a solvent. The product of formula 57 or 58 can be isolated by conventional techniques such as extraction. The ester can then be converted to a carboxylic acid of formula 4h or 4i by the method already described for conversion of formula 47 to formula 4f in scheme 19.

As outlined in Scheme 24, compounds of formula 54 can be prepared from compounds of formula 48 (see Scheme 20).

<chemistry num="35"><img file="JP4224397B2_D0035.tif" /></chemistry>

R in the formula²⁰Is C₁-C₄It is alkyl.

In this method, the hydrazine compound of formula 48 is contacted with the compound of formula 59 (fumaric acid ester or maleic acid ester or a mixture thereof may be used) in the presence of a base and a solvent. The base is typically a metal alkoxide salt such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tertiary butoxide, lithium tertiary butoxide and the like. Bases greater than 0.5 equivalents, preferably between 0.9 and 1.3 equivalents, should be used for the compound of formula 59. Compounds of formula 59 should be used that are greater than 1.0 equivalent compared to 48, preferably between 1.0 and 1.3 equivalents. Alcohol, acetonitrile, tetrahydrofuran, N, Polar protic and polar aprotic organic solvents such as N-dimethylformamide, dimethyl sulfoxide, etc. can be used. Preferred solvents are alcohols such as methanol and ethanol. It is particularly preferred that the alcohol is the same as that constituting the fumaric acid ester or maleic acid ester and the alkoxide base. The reaction is typically carried out by mixing the compound of formula 59 with a base in a solvent. The mixture can be heated or cooled to the desired temperature and the compound of formula 48 can be added over a period of time. Typically the reaction temperature is between 0 ° C and the boiling point of the solvent used. The reaction may be carried out under a pressure higher than atmospheric pressure to raise the boiling point of the solvent. Temperatures between about 30 ° C and 90 ° C are generally preferred. The addition time can be as fast as the heat transfer allows. Typical addition times are between 1 minute and 2 hours. The optimum reaction temperature and addition time will vary depending on the nature of the compounds of formulas 48 and 59. After addition, the reaction mixture can be kept at the reaction temperature for some time. Depending on the reaction temperature, the retention time required may be 0-2 hours. Typical retention time is 10-60 minutes. The reaction mass can then be acidified by adding an organic acid such as acetic acid or an inorganic acid such as hydrochloric acid or sulfuric acid. -CO of the compound of formula 54, depending on the reaction conditions and the method of isolation₂R²⁰The functional group is -CO₂It may be hydrolyzed to H, for example, the presence of water in the reaction mixture can facilitate such hydrolysis. Carboxylic acid (-CO₂If H) is formed, use the esterification method well known in the art to R.²⁰Is C₁-C₄Alkyl-CO₂R²⁰Can be converted back to. The desired product (compound of Formula 54) can be isolated by methods known to those of skill in the art, such as crystallization, extraction or distillation.

Scheme 25 depicts the general synthesis of pyro-acid of formula 4j. Treatment of the compound of formula 60 with 2,5-dimethoxytetrahydrofuran (61) gives pyrrole of formula 62. Formylation of pyrrole 62 to give the aldehyde of formula 63 is accomplished by using standard Vilsmeier-Haack formylation conditions such as N, N-dimethylformamide (DMF) and phosphorus oxychloride. Can be done. Halogenation of compounds of formula 63 with N-halosuccinimide (NXS), such as N-chlorosuccinimide or N-bromosuccinimide, occurs preferentially at the 4-position of the pyrrole ring. Oxidation of the halogenated aldehyde gives the pyrrole acid of formula 4j. Oxidation can be achieved by using various standard oxidation conditions.

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The synthesis of certain pyridinylpyrroic acids of formula 4k is depicted in Scheme 26. The compound of formula 65 (3-chloro-2-aminopyridine) is a known compound (see J. Heterocycl. Chem. 1987, 24 (5), pages 1313-16). The convenient production of 65 from 2-aminopyridine of formula 64 involves protection, ortho-metallation, chlorination and the following deprotection. The rest of the synthesis is performed according to the general synthesis illustrated in Scheme 25.

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The benzoxazinone of formula 10 can be produced by various methods. Two methods that are particularly useful are illustrated in Schemes 27-28. In Scheme 27, the benzoxazinone of formula 10 is produced directly by coupling the carboxylic acid of formula 4 with the anthranilic acid of formula 68.

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This is in sequence the addition of methanesulfonyl chloride in the presence of a tertiary amine such as triethylamine or pyridine to the carboxylic acid of formula 4, followed by the addition of anthranilic acid of formula 68, followed by the tertiary amine and methane chloride. With a second addition with sulfonyl. This method generally gives good yields of benzoxazineone.

Scheme 28 depicts an alternative production of benzoxazineone of formula 10 with coupling of the acid chloride of formula 3 to isatoic anhydride of formula 8 for direct delivery of benzoxazineone of formula 10.

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Solvents such as pyridine or pyridine / acetonitrile are suitable for this reaction. As mentioned above, the acid chloride of formula 3 is available from the corresponding acid of formula 4 by known methods such as chlorination with thionyl chloride or oxalyl chloride.

As outlined in Scheme 29, the production of isatoic anhydride of formula 8 can be achieved from isatin of formula 70.

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Isatin of formula 70 is the Journal of the Brazilian Chemical Society, FDPopp, Adv. Heterocycl. Chem. 1975, pp. 18, 1-58 and JFM Da Silva et al. , 2001, 12 (3), pp. 273-324, available from aniline derivatives of formula 69 according to literature procedures. Oxidation of isatin 70 with hydrogen peroxide generally gives a good yield of the corresponding isatin anhydride 8 (G. Reissenweber and D. Mangold, Angew. Chemie). .Int.Ed.Engl.1980, 19, pp. 222-223). Isatoic anhydride is also available from 68 by a number of known procedures involving the reaction of anthranilic acid 68 with phosgene or phosgene equivalent.

It is understood that some of the reagents and reaction conditions described above for making compounds of formula I may be incompatible with certain functionalities present in the intermediate. In these cases, incorporation of a protected / deprotected sequence or functional group interconversion into the synthesis will help to obtain the desired product. The use and selection of protecting groups will be apparent to those skilled in chemical synthesis (eg, by Greene, TW) and Wuts, PGM (Wuts, PGM), " Protective Groups in Organic See Synthesis, 2nd Edition, Wiley, New York, 1991). One of ordinary skill in the art will, in some cases, add, not described in detail, to complete the synthesis of the compound of formula I after introduction of a given reagent as depicted in any individual scheme. You will understand that it may be necessary to perform a stereotyped synthesis process. Those skilled in the art may also need to perform the combination of steps exemplified in the above scheme in an order other than that implied by the particular order presented to produce the compounds of formula I. You will also understand that.

Those skilled in the art may also use the compounds and intermediates of formula I described herein to add substituents or partially modify existing substituents in a variety of electrophilic, nucleophilic, radical, organic. You will understand that it is capable of undergoing metallic, oxidation, and reduction reactions.

It is believed that those skilled in the art using the prior art will be able to utilize the invention to its fullest extent without further detail. Therefore, the following examples should be construed as merely exemplifying the present disclosure and not limiting the present disclosure in any way. Percentages are by weight of chromatographic solvent mixture or unless otherwise specified. Parts and percentages for chromatograph solvent mixtures are by volume unless otherwise specified.¹The HNMR spectrum is reported from tetramethylsilane to the low magnetic field side in ppm, where s means singlet, d means doublet, t means triplet, q means quartet, and m means multiplet. Means, dd means doublet doublet, dt means triplet doublet, and br s means broad singlet.

Example 1 1- [2- (Hydroxymethyl) phenyl] -N- (2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl) -3- (trifluoromethyl) -1H-pyrazol-5- Manufacture of carboxamide Step A: Preparation of 1- [2- (methoxycarbonyl) phenyl] -3- (trifluoromethyl) -1H-pyrazole-5-carboxylic acid SOCl₂3 solutions of 1- [2- (methoxycarbonyl) phenyl] -3- (trifluoromethyl) -1H-pyrazole-5-carboxylic acid (8.0 g, WO 99/32545) in (100 mL). Heated and refluxed for hours. The reaction mixture was cooled and concentrated to give a crude acid chloride.

At 0 ° C, the crude acid chloride in 70 mL acetone was added dropwise to a 400 mL acetone solution of 2-amino-3-methylbenzoic acid (4.11 g) and triethylamine (8.24 g). The reaction mixture was stirred at 0 ° C. for 10 minutes and then warmed to room temperature for 1.5 hours to form the title compound of step A. The mixture containing this compound proceeded directly to step B.

Step B: 2- [5-[[[2-Methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] amino] carbonyl] -3- (trifluoromethyl) -1H-pyrazol-1- Il] Production of methyl benzoate A 70 mL acetone solution of isobutyl chloroformate (3.72 g) was added dropwise to the reaction mixture from step A. After 10 minutes, the reaction mixture was concentrated to give an orange oil. Isopropylamine (4.0 g) was added to a 500 mL acetone solution of orange oil at room temperature. After 20 minutes, the reaction mixture was concentrated and then triturated with n-chlorobutane. The white solid was collected by filtration and air dried to give the title compound (7.0 g).

Step C: 1- [2- (Hydroxymethyl) phenyl] -N- [2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -3- (trifluoromethyl) -1H-pyrazole -5-Manufacture of carboxamide A solution of lithium borohydride (2 mL, 2 M in tetrahydrofuran) was added to a solution of ester (240 mg) in tetrahydrofuran (3 mL) from step B. After stirring overnight at room temperature, the reaction was quenched with water. The reaction mixture was diluted with 1N HCl aqueous solution, extracted with ethyl acetate, washed with brine, dried and concentrated to give a white solid. The solid was washed with ethyl ether (3 x 2 mL) to give the title compound (96 mg) (product of the invention).¹1 H NMR (CDCl₃): δ9.81 (s, 1H), 7.65 (m, 1H), 7.51 (m, 1H), 7.38 (m, 1H), 7.20 (m, 5H), 5.90 (d, J = 7.42Hz, 1H) , 4.44 (s, 2H), 4.11 (m, 1H), 3.58 (br s, 1H), 2.15 (s, 3H), 1.22 (d, J = 6.9Hz, 6H).

Example 2 4-[[[1- (3-Chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazol-5-yl] carbonyl] amino] -3-methyl-5 [[(1-methylethyl) ) Amino] carbonyl] Production of methyl benzoate Step A: Production of 2-amino-5-iodo-3-methylbenzoic acid 2-Amino-3-methylbenzoic acid (10 g, 66 mmol) was dissolved in 70 mL of N, N-dimethylformamide (DMF) and treated with N-iodosuccinimide (16.4 g, 73 mmol). The mixture was heated at 60 ° C for 17 hours and allowed to cool to 25 ° C. The mixture was diluted with water (150 mL) and filtered. The air-dried solid was dissolved in ethyl acetate (200 mL) and dried over magnesium sulfate. Evaporation of the solvent gave the title compound of step A (7.95 g).¹1 H NMR (CDCl₃): δ7.87 (1H), 7.44 (1H), 2.09 (3H).

Step B: 2- [1- (3-Chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazole-5-yl] -6-iodo-8-methyl-4H-3,1-benzo Production of oxazine-4-one To methanesulfonyl chloride (1.64 g, 14.4 mmol) in acetonitrile (20 mL) at -5 ° C, 4 g (14 mmol) 1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl)-. 1H-Pyrazole-5-carboxylic acid (title compound from Example 6) and triethylamine (1.39 g, 14 mmol) were added. After 5 minutes, the title compound of Step A (3.8 g, 14 mmol) was added. After 10 minutes, triethylamine (1.39 g, 14 mmol) was added. After continuing stirring at 0 ° C. for 20 minutes, methanesulfonyl chloride (1.64 g, 14.4 mmol) was added. The mixture was allowed to warm to 25 ° C and stirred for 2 hours. The mixture was concentrated under reduced pressure and chromatographed using dichloromethane as the eluent. Appropriate fractional pooling and solvent evaporation gave the title compound of step B (3.07 g).¹1 H NMR (CDCl₃): δ8.6 (1H), 8.36 (1H), 7.98 (1H), 7.86 (1H), 7.58 (1H), 7.49 (1H), 1.79 (1H).

Step C: 1- (3-Chloro-2-pyridinyl) -N- [4-iodo-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -3- (trifluoromethyl) Production of -1H-pyrazole-5-carboxamide The title compound of Step B (3.07 g, 5.7 mmol) was dissolved in tetrahydrofuran (30 mL) and treated with isopropylamine (1.69 g, 28.7 mmol). The mixture was heated at 60 ° C. for 2 hours and concentrated to dryness under reduced pressure. The residue was chromatographed on silica gel using ethyl acetate / hexane (40:60) as the eluent. Appropriate fractional pooling and solvent evaporation gave the title compound of step C (2.4 g), melting point 199-200 ° C.¹1 H NMR (CDCl₃): δ10.3 (NH), 8.42 (1H), 7.84 (1H), 7.61 (1H), 7.44 (2H), 7.42 (1H), 6.01 (1H), 4.21 (m, 1H), 2.13 (s, 3H), 1.2 (6H).

Step D: 4-[[[1- (3-Chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazol-5-yl] carbonyl] amino] -3-methyl-5-[[( Production of 1-methylethyl) amino] carbonyl] methyl benzoate The title compound of Step C (2.4 g, 4 mmol) was dissolved in dimethyl sulfoxide (30 mL) with methanol (2 mL) and triethylamine (1 mL). Palladium acetate (0.05 g) and bis (diphenylphosphinopropane) (0.10 g) were added. Carbon monoxide was bubbled into the solution for 5 minutes. The mixture was heated at 70 ° C. for 6 hours under a carbon monoxide rubber balloon. The cooled reaction mixture was poured into water (50 mL). The resulting solid was collected by filtration, dissolved in ether and dried over magnesium sulphate. The residue after solvent distillation was chromatographed on silica gel using ethyl acetate / hexane (30:70) as the eluent. Appropriate fractional pooling and solvent evaporation gave the title compound of step D (compound of the invention) (1.71 g), melting point 204-206 ° C.¹1 H NMR (CDCl₃): δ10.8 (NH), 8.51 (1H), 7.92 (1H), 7.90 (1H), 7.41 (1H), 7.39 (1H), 6.15 (1H), 4.21 (1H), 3.92 (1H), 2.23 (1H), 1.26 (6H).

Example 3 N- [4-Acetyl-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H- Production of pyrazole-5-carboxamide Example 2, the title compound of Step C (0.7 g, 1.3 mmol) was dissolved in DMF (10 mL) to tributyl- (1-ethoxyvinyl) tin (0.47 g, 1.3 mmol) and bis (triphenylphosphine) palladium. Treated with dichloride (50 mg). The mixture was heated at 80 ° C. for 4 hours. The mixture was poured into water (50 mL) and extracted with ether (3 x 50 mL). The combined organic layers were washed with water (50 mL) and saturated brine (50 mL). The mixture was dried over magnesium sulfate and concentrated under reduced pressure. The residue was filtered through a silica gel cartridge using dichloromethane as the eluent. Appropriate fractions were pooled and evaporated. The residue (400 mg) was dissolved in acetone (20 mL) and treated with 1N hydrochloric acid (5 mL). After 1 hour at 25 ° C., the reaction mixture was partitioned between ethyl acetate (50 mL) and water (50 mL). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The residue was chromatographed on silica gel using ethyl acetate / hexane (40:60) as the eluent. Appropriate fractional pooling and solvent evaporation gave the title compound (compound of the invention) (150 mg) as a yellow solid, melting point 135-137 ° C.¹1 H NMR (CDCl₃): δ10.8 (NH), 8.42 (1H), 7.89 (1H), 7.87 (2H), 7.42 (1H), 7.31 (1H), 6.15 (1H), 4.21 (1H), 2.59 (3H), 2.27 (3H), 1.28 (6H).

Example 4 N- [4-Amino-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H- Production of pyrazole-5-carboxamide Step A: Production of 3-Methyl-5-Nitroisatoic anhydride Potassium nitrate (1.43 g, 14.1 mmol) was added little by little to a solution of 3-methylisatoic anhydride (2.50 g, 14.1 mmol) and concentrated sulfuric acid (8 mL) below 30 ° C while cooling in an external water bath. The resulting mixture was stirred at 25 ° C for 1.5 hours and then poured into approximately 200 g of ice with stirring. After the ice had melted, the solid product was isolated by filtration, washed with dilute aqueous HCl and then air dried. The product was suspended in acetonitrile (50 mL) and concentrated in vacuo to give 2.75 g of a yellow solid.¹H NMR (DMSO-d₆): δ11.6 (br s, 1H), 8.45 (d, 1H), 8.42 (d, 1H), 2.43 (s, 3H).

Step B: 2- [1- (3-Chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazole-5-yl] -8-methyl-6-nitro-4H-3,1-benzo Oxazine-4-one Title substance from step A of 505 mg (1.63 mmol), 344 mg (1.55 mmol) 1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazole-5-carbonyl chloride (Example) A mixture of (7) and 2 mL of pyridine was heated at 100 ° C. for 3 hours. The resulting mixture was cooled to 25 ° C and partitioned between ethyl acetate and dilute aqueous hydrochloric acid solution. The organic layer was washed 3 times with dilute aqueous hydrochloric acid solution, dried over anhydrous magnesium sulfate and concentrated to give the brown solid used in the next step without further purification.¹1 H NMR (CDCl₃): δ8.86 (d, 1H), 8.60 (dd, 1H), 8.38 (d, 1H), 8.03 (dd, 1H), 7.59 (s, 1H), 1.95 (s, 3H).

Step C 1- (3-Chloro-2-pyridinyl) -N- [2-methyl-6-[[(1-methylethyl) amino] carbonyl] -4-nitrophenyl] -3- (trifluoromethyl)- Production of 1H-pyrazole-5-carboxamide Isopropylamine (0.35 mL, 4.11 mmol) was added to a solution of 619 mg (1.37 mmol) of the product of Step B in dioxane (8 mL) at 25 ° C. After stirring overnight, the resulting heterogeneous mixture was concentrated and the residue was triturate with methanol (10 mL). Filtration gave 100 mg of the title product. The filtrate was concentrated and the resulting residue was triturated with diethyl ether. Filtration of the resulting solid gave an additional 320 mg of the title product, melting point 170-172 ° C.

Step D: N- [4-amino-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) Production of -1H-pyrazole-5-carboxamide Zinc fines (90 mg, 1.4 mmol) were added to a solution of the product from step C (70 mg, 0.14 mmol) and trifluoroacetic acid (2 mL) at 70 ° C. Some bubbling occurred. After 10 minutes at 70 ° C, the mixture was cooled to 25 ° C, diluted with dichloromethane and filtered. The filtrate was concentrated to distill off most of the trifluoroacetic acid and the resulting residue was dissolved in acetonitrile (3 mL) and 1,2-dichloroethane (3 mL). The resulting solution is a strong basic ion exchange resin (Dowex® 550A, OH).^-Form, treated with 2 g), shaken for 1 hour, then filtered. Concentration of the filtrate gave the title compound (compound of the invention) as a yellow solid.¹1 H NMR (CDCl₃): δ9.80 (br s, 1H), 8.50 (dd, 1H), 7.82 (dd, 1H), 7.42 (s, 1H), 7.39 (m, 1H), 6.50 (br d, 2H), 6.02 ( m, 1H), 2.10 (s, 3H), 1.11 (d, 6H).

Example 5 N- [4-benzoylamino-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H -Manufacture of pyrazole-5-carboxamide A solution of the title product of Example 4 (100 mg, 0.21 mmol), benzoic anhydride (52 mg, 0.23 mmol) and DMF (2 mL) was stirred at 25 ° C. overnight. The resulting mixture was concentrated under vacuum and the resulting crude product was triturated with diethyl ether and filtered to give 92 mg of the title material (compound of the invention) as a solid.¹H NMR (DMSO-d₆): δ10.36 (s, 1H), 10.22 (s, &lt;1H), 8.56 (d, 1H), 8.21 (d, 1H), 7.98-7.92 (m, 3H), 7.82 (twisted s, 1H) , 7.78 (s, 1H), 7.70-7.50 (m, 5H), 3.93 (septet, 1H), 2.18 (s, 1H), 1.03 (d, 6H).

Example 6 Step A: Production of 3-chloro-2 (1H) -pyridinone (2,2,2-trifluoro-1-methylethylidene) hydrazone 1,1,1-Trifluoroacetone (7.80 g, 69.6 mmol) was added to (3-chloro-pyridin-2-yl) -hydrazine (10 g, 69.7 mmol) at 20-25 ° C. After the addition was complete, the mixture was stirred for about 10 minutes. The solvent was evaporated under reduced pressure and the mixture was partitioned between ethyl acetate (100 mL) and saturated sodium carbonate solution (100 mL). The organic layer was dried and evaporated. Chromatography on silica gel (eluted with ethyl acetate) gave the product (11 g, 66% yield), melting point 64-64.5 ° C (after crystallization from ethyl acetate / hexane) as an off-white solid. IR (Nujor) ν 1629, 1590, 1518, 1403, 1365, 1309, 1240, 1196, 1158, 1100, 1032, 992, 800 cm^-1。¹1 H NMR (CDCl₃) δ2.12 (s, 3H), 6.91 to 6.86 (m, 1H), 7.64 to 7.61 (m, 1H), 8.33 to 8.32 (m, 2H). MS m / z 237 (M⁺)。

Process B: Manufacture of ethyl hydrogen ethanedioate (3-chloro-2-pyridinyl) (2,2,2-trifluoro-1-methylethylidene) hydrazide Triethylamine (20.81 g, 0.206 mol), 3-chloro-2 (1H) -pyridinone (2,2,2-trifluoro-1-methylethylidene) hydrazone in dichloromethane (68 mL) (ie, product of step A) ) (32.63 g, 0.137 mol) at 0 ° C. Ethyl chlorooxoacetate (18.75 g, 0.137 mol) in dichloromethane (69 mL) was added dropwise to the mixture at 0 ° C. The mixture was allowed to warm to 25 ° C for about 2 hours. The mixture was cooled to 0 ° C and an additional portion of ethyl chlorooxoacetate (3.75 g, 27.47 mmol) in dichloromethane (14 mL) was added dropwise to the mixture at 0 ° C. After about 1 hour of addition, the mixture was diluted with dichloromethane (about 450 mL) and the mixture was washed with water (2 x 150 mL). The organic layer was dried and evaporated. Chromatography on silica gel (eluted with 1: 1 ethyl acetate-hexane) gives the product as a solid (42.06 g, 90% yield), melting point 73.0-73.5 ° C (after crystallization from ethyl acetate / hexane). It was.

IR (Nujor) ν 1751, 1720, 1664, 1572, 1417, 1361, 1330, 1202, 1214, 1184, 1137, 1110, 1004, 1043, 1013, 942, 807, 836 cm^-1。¹H NMR (DMSO-d₆, 115 ° C) δ 1.19 (t, 3H), 1.72 (br s, 3H), 4.25 (q, 2H), 7.65 (dd, J = 8.3, 4.7Hz, 1H), 8.20 (dd, J = 7.6, 1.5Hz, 1H), 8.55 (d, J = 3.6Hz, 1H). MS m / z 337 (M⁺)。

Process C: Production of ethyl 1- (3-chloro-2-pyridinyl) -4,5-dihydro-5-hydroxy-3- (trifluoromethyl) -1H-pyrazole-5-carboxylate Ethyl hydrogen ethanedioate (3-chloro-2-pyridinyl) (2,2,2-trifluoro-1-methylethylidene) hydrazide in dimethyl sulfoxide (25 mL) (ie, product of step B) (5 g, 14.8) Methyl) was added to tetrabutylammonium fluoride hydrate (10 g) in dimethyl sulfoxide (25 mL) over 8 hours. When the addition was complete, the mixture was poured into a mixture of acetic acid (3.25 g) and water (25 mL). After stirring overnight at 25 ° C., the mixture was then extracted with toluene (4 x 25 mL) and the combined toluene extracts were washed with water (50 mL), dried and evaporated to give a solid. Chromatography on silica gel (eluted with 1: 2 ethyl acetate-hexane) as a solid product (2.91 g, 50% yield, about 5% 3-chloro-2 (1H) -pyridinone (2,2, It contained 2-trifluoro-1-methylethylidene) hydrazone) and was given a melting point of 78-78.5 ° C (after crystallization from ethyl acetate / hexane).

IR (Nujor) ν 3403, 1726, 1618, 1582, 1407, 1320, 1293, 1260, 1217, 1187, 1150, 1122, 1100, 1067, 1013, 873, 829 cm^-1。¹1 H NMR (CDCl₃) δ 1.19 (s, 3H), 3.20 (1/2 of ABZ pattern, J = 18Hz, 1H), 3.42 (1/2 of ABZ pattern, J = 18Hz, 1H), 4.24 (q, 2H), 6.94 ( dd, J = 7.9, 4.9Hz, 1H), 7.74 (dd, J = 7.7, 1.5Hz, 1H), 8.03 (dd, J = 4.7, 1.5Hz, 1H). MS m / z 319 (M⁺)。

Step D: Production of ethyl 1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazole-5-carboxylate Sulfuric acid (concentrated, 2 drops) in 1- (3-chloro-2-pyridinyl) -4,5-dihydro-5-hydroxy-3- (trifluoromethyl) -1H-pyrazol-5 in acetic acid (10 mL) -Ethyl carboxylate (ie, product of step C) (1 g, 2.96 mmol) was added and the mixture was warmed to 65 ° C for about 1 hour. The mixture was allowed to cool to ° C and most of the acetic acid was distilled off under reduced pressure. The mixture was partitioned between saturated aqueous sodium carbonate solution (100 mL) and ethyl acetate (100 mL). The aqueous layer was further extracted with ethyl acetate (100 mL). The combined organic extracts were dried and evaporated to give the product (0.66 g, 77% yield) as an oil. IR (neat) ν 3147, 2986, 1734, 1577, 1547, 1466, 1420, 1367, 1277, 1236, 1135, 1082, 1031, 973, 842, 802 cm^-1。¹1 H NMR (CDCl₃) δ1.23 (t, 3H), 4.25 (q, 2H), 7.21 (s, 1H), 7.48 (dd, J = 8.1, 4.7Hz, 1H), 7.94 (dd, J = 6.6, 2Hz, 1H) , 8.53 (dd, J = 4.7, 1.5Hz, 1H). MS m / z 319 (M⁺)。

Step E: Production of 1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazole-5-carboxylic acid Potassium hydroxide (0.5 g, 85%, 2.28 mmol) in water (1 mL), 1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazole in ethanol (3 mL) It was added to ethyl -5-carboxylate (ie, the product of step D) (0.66 g, 2.07 mmol). After about 30 minutes, the solvent was evaporated under reduced pressure and the mixture was dissolved in water (40 mL). The solution was washed with ethyl acetate (20 mL). The aqueous layer was acidified with concentrated hydrochloric acid and extracted with ethyl acetate (3 × 20 mL). The combined extracts were dried and evaporated to give the product as a solid (0.53 g, 93% yield), melting point 178-179 ° C (after crystallization from hexane-ethyl acetate).

IR (Nujor) ν 1711, 1586, 1565, 1550, 1440, 1425, 1292, 1247, 1219, 1170, 1135, 1087, 1059, 1031, 972, 843, 816 cm^-1。¹H NMR (DMSO-d₆) δ7.61 (s, 1H), 7.77 (m, 1H), 8.30 (d, 1H), 8.60 (s, 1H).

Example 7 Production of 1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazole-5-carbonyl chloride 268 mg (0.92 mmol) 1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazol-5-carboxylic acid in 5 mL of dichloromethane (can be prepared according to Example 6) To add 160 μL (1.84 mmol) of oxalyl chloride and 2 drops of DMF in sequence at room temperature. The mixture was then stirred at the same temperature for about 1 hour. The crude mixture was then concentrated under vacuum. The title material is typically used without additional purification or characterization.

The following compounds in Tables 1-5 can be prepared by the procedures described herein along with methods known in the art. The following abbreviations are used in the table. t means third, s means second, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl. , Pr means propyl, Bu means butyl, i-Pr means isopropyl, t-Bu means tertiary butyl, Ph means phenyl, OMe means methoxy, EtO Or OEt means ethoxy, SMe means methylthio, SEt means ethylthio, CN means cyano, NO₂Means nitro, MeSO means methylsulfinyl, and MeSO₂Means methylsulfonyl.

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Formulation / Practical The compounds of the present invention will generally be used as agriculturally suitable carrier-containing formulations or compositions containing at least one liquid diluent, solid diluent or surfactant. The formulation or composition component is selected to be compatible with the physical properties of the active ingredient, the method of application and environmental factors such as soil type, humidity and temperature. Useful formulations include liquids such as solutions (including emulsifying concentrates), suspensions, emulsifiers (including microemulsions and / or saspo emulsions) that can optionally be thickened into gels. .. Useful formulations further include solids such as fine powders, powders, granules, pellets, tablets, films, etc. that can be water dispersible (wet) or water soluble. The active ingredient can be (micro) encapsulated and further formed into a suspension or solid formulation, or the entire formulation of the active ingredient is encapsulated (or "overcoated"). be able to. Encapsulation can suppress or delay the release of the active ingredient. The sprayable formulation can be increased in a suitable medium and used in a spray volume of about 1 to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.

The formulation typically contains an effective amount of active ingredient, diluent and surfactant within the following approximate range totaling 100% by weight.

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Typical solid diluents are published in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Edition, Dorland Books, Caldwell, NJ. Are listed. Typical liquid diluents are described by Marsden, Solvents Guide, 2nd Edition, Interscience, New York, 1950. "McCutcheon's Detergents and Emulsifiers Annual", Allured Publ., Ridgewood, NJ, and Sisely and Wood, "Encyclopedia of Surface Active Agents" (Surfactant Encyclopedia) , Chemical Publ., New York, 1964 lists surfactants and recommended applications. All formulations can contain small amounts of additives to reduce foaming, cake formation, corrosion, microbial growth, etc., or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohol, polyethoxylated alkylphenol, polyethoxylated sorbitan fatty acid ester, sulfosuccinate dialkyl salt, alkyl sulfate, alkylbenzene sulfonate, organosilicon, N, N-dialkyltaurate. , Ligno sulfonate, surfactant sulfonate formaldehyde condensate, polycarboxylic acid salt, and polyoxyethylene / polyoxypropylene block copolymer. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapargite and kaolin, starch, sugar, silica, talc, diatomaceous soil, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. .. Liquid diluents include, for example, water, N, N-dimethylformamide, dimethylsulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, olive oil, castor oil, linseed oil, tung oil, sesame oil, etc. Ketones such as corn oil, peanut oil, cotton seed oil, soybean oil, rapeseed oil, and coconut oil, fatty acid esters, cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, as well as methanol, cyclohexanol. , Decanol and alcohols such as tetrahydrofurfuryl alcohol.

Solutions containing emulsifying concentrates can be made by simply mixing the ingredients. Fines and powders can be produced by blending and grinding, usually as in a hammer mill or fluid energy mill. Suspensions are usually made by wet grinding, see, for example, US Pat. No. 3,060,084. Granules and pellets can be produced by spraying the active substance onto preformed granule carriers or by agglomeration techniques. Browning, "Agglomeration," Chemical Engineering, December 4, 1967, pp. 147-48, "Perry's Chemical Engineer's." See Handbook, 4th Edition, McGraw-Hill, New York, 1963, pp. 8-57 and sequel, as well as PCT Publication, International Publication No. 91/13546. Pellets can be produced as described in US Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be produced as taught in US Pat. Nos. 4,144,050, 3,920,442 and DE 3,246,493. Tablets can be manufactured as taught in US Pat. Nos. 5,180,587, 5,232,701 and 5,208,030. Films can be produced as taught in UK Pat. No. 2,095,558 and US Pat. No. 3,299,566.

For more information on compounding techniques, see The Formulator's Toolbox, by TS Woods, Pesticide Chemistry and Bioscience, The Food-Environment Challenge. Proceedings of the 9th International Congress on Pesticide Chemistry, edited by T. Brooks and TR Roberts, Product Forms for Modern Agriculture. (Newsletter of the 9th International Society of Insecticide Chemistry) ", The Royal Society of See Chemistry, Cambridge, 1999, pp. 120-133. Also, U.S. Pat. Nos. 3,235,361, Column 6, Rows 16 to Columns 7, Rows 19 and Examples 10-41; U.S. Pat. Nos. 3,309,192, Columns 5, Rows 43 to Columns 7, Rows 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. Pat. No. 2,891,855; Column 3, Row 66 to Column 5, Row 17, and Examples See also 1-4. Klingman, Weed Control as a Science, John Wiley and Sons, New York, 1961, pp. 81-96; and Hance et al., Weed Control Handbook ( See also Weed Control Handbook), 8th Edition, Blackwell Scientific Publications, Oxford, 1989.

In the following examples, all percentages are by weight and all formulations are prepared in the usual way. Compound numbers relate to the compounds in Index Table A.

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The compounds of the present invention are characterized by favorable metabolic and / or soil residue patterns and exhibit activity in controlling a range of agricultural and non-agricultural invertebrate pests (in the context of this specification, "invertebrate pests". "Control" means the prevention of vertebrate pest outbreaks (including death), which results in a significant reduction in invertebrate ingestion or other injuries or damages caused by invertebrate pests. Related expressions are similar. Defined as). As mentioned herein, the term "invertebrate pest" includes arthropods, abdominal animals and nematodes that are economically important as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, woodlouse and binders. The term "belly-footed animal" includes Stylommatophora, slugs and other slugs. The term "nematode" includes all parasites such as roundworms, cordworms and phytophagous nematodes (C. elegans), trematodes (C. elegans), ascaris and tapeworms (Tapeworms). To do. Those skilled in the art will recognize that not all compounds are equally effective against all pests. The compounds of the present invention are active against economically important agricultural and non-agricultural pests. The term "agricultural" relates to the production of crops such as for food and fiber, and involves cereal crops (eg wheat, oat, barley, rye, rice, corn), soybeans, vegetable crops (eg lettuce, cabbage). , Tomatoes, legumes), potatoes, sweet potatoes, grapes, cotton, and fruit trees (eg, pear fruits, stone fruits and citrus fruits). The term "non-agricultural" refers to other horticulture (eg, forests, greenhouses, nurseries or ornamental plants that do not grow on cultivated land), public (human) health and animal health, home and commercial structures, homes, and storage product applications or. Related to pests. Invertent Pest Control For crops such as cotton, corn, soybeans, rice, vegetable crops, potatoes, sweet potatoes, grapes and fruits (invertent pests) by controlling invertent pests due to spectrum and economic importance. Damage caused by Protection (or from damage) is a preferred embodiment of the invention. Agricultural or non-agricultural pests include armyworms, armyworms, inchworms and tobacco moths within the family Noctuidae (eg, a species of armyworm (Spodoptera fugiperda JE). Razoumowsky))), the larvae of the family Click Beetle, the family Click Beetle, the family of the family Click Beetle, and the family of the family Click Beetle. In addition, agricultural and non-agricultural pests include adult and larvae of the order Psyllidae, including the scale insects of the strain Forficulidae (eg, Forficula auricularia Linnaeus, Chelisoches morio Fabricius), Psyllidae. Adults and juveniles of the order Hemiptera and Psyllidae, such as the scale insects of the scale insects, semis of the strain group Psyllidae, the strains of the strain group Psyllidae (eg, Empoasca spp.) Hemiptera, Psyllidae, Psyllidae, Psyllidae, Psyllidae, Psyllidae, Psyllidae, Psyllidae, Psyllidae, Psyllidae Scale insects of the family Psyllidae, scale insects of the family Psyllidae, scale insects of the family Psyllidae and Psyllidae, scale insects of the family Psyllidae, turtles of the family Psyllidae, cinch bugs of the family Psyllidae (eg, Blissus spp. ) And other seed bugs, the froghopper of the clade froghopper, the leaf-footed bug of the clade froghopper, and the froghopper and the froghopper of the clade froghopper. Strains Adults and larvae of the order mites (mites) such as spider mite and red spider mite (eg, Panonychus ulmi Koch), Nami spider mite (Tetranychus urticae Koch), McDaniel mites (Tetranychus mcdanieli McGregor), Strains Flatmite of the spider mite family (eg, Brevipalpus lewisi McGregor), sabi mites and bad mites within the lineage group Fushidani family and other leaf-eating mites and mites important to human and animal health, ie strains. Chili mites in the group Leopard mite family, acne mites in the lineage group Spider mite family, wheat mites in the lineage group spider mite, ticks in the order ticks (for example, one of the ticks of the genus Ixodes scapularis Say), Australian paralytics (Ixodes) holocyclus Neumann), American dog tick (Dermacentor variabilis Say), American Ambrioma (Amblyomma americanum Linnaeus), and strains including scabmite and mites within the spider mite family, spider mite family and spider mite family, mites, butterflies, locusts, crickets. Adults and larvae of the order Spider mite (eg, mobile mites (eg, Melanoplus sanguinipes Fabricius, M.). Also included are pests of the order Siphonoptera, including flea (Echidnophaga gallinacea Westwood), human fleas (Pulex irritans Linnaeus) and other fleas that plague mammals and birds. Other arthropod pests included include spider spiders such as the brown recluse spider (Loxosceles reclusa Gertsch &amp; Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and the centipede (Scutigera coleoptrata Linnaeus). Examples include eye spiders. The compounds of the present invention are economically important agricultural pests (ie, nematodes nematodes in the genus Nematode, lesion nematodes in the genus Negusare nematodes, stubby root nematodes in the genus Trichodras, etc.) and animals and humans. Economically important health pests (ie Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in worms, etc. Not limited to all trematodes, tapeworms, roundworms,), but includes economically important members of the roundworm subjects such as roundworms, pinworms, nematodes, nematodes, nematodes, and enobules. It is active against members of nematodes, tapeworms, trematodes and pinworms. Examples include arachnid spiders such as Mulaik) and black widow (Latrodectus mactans Fabricius), and centipedes such as Centipede (Scutigera coleoptrata Linnaeus). The compounds of the present invention are economically important agricultural pests (ie, nematodes nematodes in Nematode nematodes, lesion nematodes in Negusare nematodes, stubby root nematodes in Trichodras, etc.) and animals and humans. Economically important health pests (ie Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in worms, etc. Not limited to all trematodes, tapeworms, roundworms,), but includes economically important members of the roundworm subjects such as roundworms, pinworms, nematodes, nematodes, nematodes, and enobules. It is active against members of nematodes, tapeworms, trematodes and pinworms.

The compounds of the present invention include the order Codling Moth (eg, Alabama argillacea Huebner), Helicoverpa armigera (Archips argyrospila Walker), Helicoverpa armigera (A. rosana Linnaeus) and other Archips species, Chilo suppressalis. Walker, Codling moth (Cnaphalocrosis medinalis Guenee), Larva of Hamshimodoki (Crambus caliginosellus Clemens), Crambus teterrellus Zincken, Codling moth (Cydia pomonella Linnaeus), Codling moth (Cydia pomonella Linnaeus) (Helicoverpa armigera hubner), Codling moth larva (Helicoverpa zea) Boddie, Heliothis virescens Fabricius, Herpetogramma licarsisalis Walker, Lobesia botrana Denis &amp; Schiffermueller, Pectinophora gossypiella Saunders, Pectinophora gossypiella Saunders brassicae Linnaeus, Cabbage White (Pieris rapae Linnaeus), Diamondback Moth (Plutella xylostella Linnaeus), Beet Armyworm (Spodoptera exigua Huebner), Spodoptera litura Fabricius, Spodoptera litura Fabricius, Spodoptera litura Fabricius It is particularly active against pests in Huebner) and a species of Twirler moth (Tuta absoluta Meyrick). The compounds of the present invention include pea aphids (Acyrthisiphon pisum Harris), bean aphids (Aphis craccivora Koch), bean aphids (Aphis fabae Scopoli), cotton aphids (Aphis gossypii Glover), apple aphids (Aphis pomi De Geer), and apple aphids (Aphis pomi De Geer). Aphis spiraecola patch, potato aphid (Aulacorthum solani Kaltenbach), strawberry aphid (Chaetosiphon fragaefolii Cockerell), Russian comgia aphid (Diuraphis noxia Kurdjumov / Mordvilko), rose apple aphid (Dyuraphis noxia Kurdjumov / Mordvilko) lanigerum Hausmann), Momokofuki aphid (Hyalopterus pruni Geoffroy), Fake aphid (Lipaphis erysimi Kaltenbach), Grain aphid (Metopolophium dirrhodum Walker), Tulip aphid (Macrosipum euphorbiae Thomas) Lettuce aphids (Nasonovia ribisnigri Mosley), Kobu aphids (Pemphigus spp.), Corn aphids (Rhopalosiphum maidis Fitch), Wheat aphids (Rhopalosiphum padi Linnaeus), Wheat aphids (Schizaphis graminum Rondani) , Madara aphid aphid (Therioaphis) maculata Buckton, Toxoptera aurantii Boyer de Fonscolombe and Toxoptera citricida Kirkaldy, Adelges spp., Phylloxera devastatrix Pergande, Whitefly, Whitefly Whitefly (Bemisia argentifolii Bellows &amp; Perring), Whitefly (Dialeurodes citri Ashmead) and Greenhouse Whitefly (Trialeurodes vaporariorum Westwood), Potato Himeyokobai (Empoasca fabae Harris), Himetobiunka (Laodelphax Fall) Forbes, leafhopper (Nephotettix cinticeps Uhler), green leafhopper (Nephotettix nigropictus Stal), brown planthopper (Nilaparvata lugens Stal), corn planthopper (Peregrinus maidis Ashmead), scale insect (Sogatella furcifera) Leafhopper (Typhlocyba pomaria McAtee), Chimadarahime Yokobai (Erythroneoura spp.), Seventeenth year seminar (Magcidada septendecim Linnaeus), Iseriya purchasi Maskell, Sanhose scale insect (Quadraspidiotus pernicus) It also has commercially important activity on members of the order Hemiptera, including Risso), other scale insects (Pseudococcus spp.), European Psyllidae (Cacopsylla pyricola Foerster), and Psyllidae (Trioza diospyri Ashmead). These compounds include the stink bug (Acrosternum hilare Say), the leaf-footed bug (Anasa tristis De Geer), the stink bug (Blissus leucopterus leucopterus Say), the cotton lace bug (Corythuca gossypii Fabricius), and the tomato bug (Cyrtopeltis mode). , Dysdercus suturellus Herrich-Schaeffer, a kind of brown stink bug (Euchistus servus Say), Itten stink bug (Euchistus variolarius Palisot de) Beauvois), Yellow spotted stink bug (Graptosthetus spp.), Leaf-footed bug (Leptoglossus corculus Say), Green stink bug (Lygus lineolaris Palisot de Beauvois), Southern green stink bug (Nezara viridula Linnaeus) It is also active in the members of the order Hemiptera, including one of the species (Oncopeltus fasciatus Dallas) and the southern green stink bug (Pseudatomoscelis seriatus Reuter). Other insects controlled by the compounds of the invention include thrips (eg, French thrips (Frankliniella occidentalis Pergande), Western flower thrips (Scirthothrips citri Moulton), soybean thrips (Sericothrips variabilis Beach) and thrips (Thrips variabilis Beach). tabaci Lindeman), as well as other Coleoptera (eg, Colorado potato beetle (Leptinotarsa decemlineata Say), Mexican bean beetle (Epilachna varivestis Mulsant) and Agriotes, Athous or Limonius larvae Can be mentioned.

One or more of growth regulators such as rooting stimulants, chemical fertility agents, information substances, repellents, attractants, pheromones, feeding stimulants, other bioactive compounds or insectogenic bacteria, viruses or fungi It can also be mixed with other bioactive compounds or agents. Accordingly, the compositions of the present invention may further comprise a biologically effective amount of at least one other biologically active compound or agent. Examples of such bioactive compounds or agents that can be combined with the compounds of the invention are abamectin, acephate, acetamiprid, amidoflumeth (S-1955), avelmectin, azadilactin, azinephos-methyl, bifentrin, bifenazate, buprofezin, carbofuran. , Chlorpyrifos, Chlorpyrifos-Methyl, Chlorpyrifos, Chlorpyrifos-Methyl, Chromaphenozide, Crotianidin, Cyfluthrin, Beta-Cyfluthrin, Sihalothrin, Lambda-Cihalothrin, Cipermethrin, Siromadine, Deltamethrin, Diafentiulone, Diadinone, Dimethoate dimethoate Emamectin, Endosulfane, Esfenvalerate, Ethiprol, Phenoticalve, Phenoxycarb, Fenpropatrin, Fenproximate, Fenvalerate, Fipronil, Flonicamid, Flucitrinate, Tau-Fluvalinate, Fluphenoxlon, Phonophos, Halophenozide, Hexaflumuron , Imidacloprid, Indoxacarb, Isophenphos, Ruphenuron, Malathion, Metaaldehyde, Metaamidephos, Metidetion, Metmil, Metoprene, methoxychlor, Monochromotophos, methoxyphenozide, Nitiadin, Novallon, Noviflumron (XDE-007), Oxamil, Parathion, Parathion-Methyl Permethrin, holate, hosalon, hosmet, phosphamiden, pyrimicalve, profenophos, pimetrodin, pyridalyl, pyriproxyfen, rotenon, spinosad, spiro6476), pyryphenox, pyracrostrobin, pyrimethanyl, pyrochyron, quinoxyphene, spiroxamine, sulfur, tebuconazole, tetraconazole, thiabendazole, tifluzamide, thiophanate-methyl, tiram, thiazinyl, triazimefone, triazimenol, tricyclazole, trifluxist Antifungal agents such as robin, triticonazole, validamycin and vinclozoline, aldicarb, oxamil, clothiazoben / benclothiaz, nematode repellents such as fenamiphos, fungicides such as streptomycin, amidoflumeth, amitraz, quinomethionate, chloro Acaricides such as benzilate, sihexatin, dicofol, dienochlor, etoxazole, phenazakin, fenbutatin oxide, fenpropatrin, phenpyroximate, hexithiax, propargite, pyridaben and tebufenpyrado, as well as ssp. Aizawai and kurstaki. Biologics such as Bacillus thuringiensis, Bacillus thuringiensis, Bacillus thuringiensis, baculovirus, and insectogenic fungi, viruses and fungi. The compounds of the present invention and their compositions can be applied to genetically transformed plants to exhibit protein toxicity against invertebrate plague (such as Bacillus bacillus turingiensis toxin). The effects of the exogenously applied invertebrate plague control compounds of the present invention may be synergistic with the expressed toxin proteins. In biologics such as Bacillus thuringiensis, Bacillus thuringiensis, Bacillus thuringiensis, baculovirus, and insectogenic bacteria, viruses and fungi, including aizawai and kurstaki. is there. The compounds of the present invention and compositions thereof can be applied to genetically transformed plants to exhibit protein toxicity against invertebrate plague (such as Bacillus bacillus turingiensis toxin). The effects of the exogenously applied invertebrate plague control compounds of the present invention may be synergistic with the expressed toxin proteins. In biologics such as Bacillus thuringiensis, Bacillus thuringiensis, Bacillus thuringiensis, baculovirus, and insectogenic bacteria, viruses and fungi, including aizawai and kurstaki. is there. The compounds of the present invention and their compositions can be applied to genetically transformed plants to exhibit protein toxicity against invertebrate plague (such as Bacillus bacillus turingiensis toxin). The effects of the exogenously applied invertebrate plague control compounds of the present invention may be synergistic with the expressed toxin proteins.

General references to these agricultural protectants can be found in The Pesticide Manual, 12th Edition, edited by CDS Tomlin, British Crop Protection Council. ), Farnham, Surrey, United Kingdom, 2000.

Preferred insecticides and tick control agents to be mixed with the compounds of the present invention include pyrethroids such as cipermethrin, sihalothrin, cyfluthrin, beta-cyfluthrin, esphenvalerate, fenvalerate and tralomethrin; Carbamate such as; neonicotinoids such as clothianidin, imidacloprid and thiacloprid; neurosodium channel blockers such as indoxacarb; insecticidal macrocyclic lactones such as spinosad, abamectin and emamectin; Includes γ-aminobutyric acid (GABA) antagonists; insecticidal ureas such as fluphenoxlon and triflumron; immature hormone mimics such as diofenolan and pyrethronil; pimetrodin; as well as amitraz. Preferred biopharmaceuticals to mix with the compounds of the invention include Bacillus bacillus turingiensis and Bacillus bacillus turingiensis deltaendotoxin and naturally occurring members of the Baculoviridae family as well as insectogenic fungi And genetically modified viral pesticides are included.

The most preferable mixtures include a mixture of the compound of the present invention and sihalothrin, a mixture of the compound of the present invention and beta-cifluthrin, a mixture of the compound of the present invention and esphenvalerate, and a compound of the present invention and esphenvalerate. Mixture, mixture of compound of the present invention and mesomil, mixture of compound of the present invention and imidacloprid, mixture of compound of the present invention and thiacloprid, mixture of compound of the present invention and indoxacarb, compound of the present invention and abamectin Mixtures with, compounds of the invention with endosulfan, compounds of the invention with ethiprol, compounds of the invention with fipronil, compounds of the invention with fluphenoxlon, compounds of the invention And pyriproxyfen, a compound of the present invention and pimetrodin, a mixture of the compound of the present invention and Amitraz, a mixture of the compound of the present invention and Bacillus turingiensis, and a compound of the present invention and Bacillus chew. Contains a mixture with lingiensis delta endotoxin.

Notable are compositions of the invention comprising Formula I constituents (and any surfactant and / or diluent) plus at least one additional compound or agent for controlling invertebrate pests. .. In certain cases, combinations with other invertebrate pest control compounds or agents having similar control spectra but different modes of action may be particularly advantageous for resistance management. Accordingly, the compositions of the present invention may further comprise at least one additional biologically effective amount of invertebrate pest control compound or agent having a similar control spectrum but different modes of action. it can. Contacting a plant or plant locus genetically mutated to express a plant protection compound (eg, a protein) with a biologically effective amount of a compound of the invention also provides a broader spectrum of plant protection. Can be provided, which can be advantageous for resistance management.

Invertebrate pests are an effective amount of pests in agricultural and non-agricultural applications, in the environment of pests, including rampant agricultural and / or non-agricultural areas, in areas to be protected, or directly to pests to be controlled. It is controlled by applying the above compound of the present invention. Accordingly, the present invention is a method for controlling invertent pests in agricultural and / or non-agricultural applications, which comprises one or more compounds of the present invention in a biologically effective amount of the invertent pests or their environment. And, or contact with a composition comprising at least one such compound or a composition comprising at least one such compound and an effective amount of at least one additional biologically active compound or agent. It further includes methods that include such things. Examples of suitable compositions comprising a compound of the invention and an effective amount of at least one additional biologically active compound or agent are such that the additional biologically active compound or agent is a compound of the invention. Examples thereof include granular compositions present in the same granules as, or in granules separate from those of the compounds of the invention.

The preferred method of contact is by spraying. Alternatively, the granular composition containing the compound of the present invention can be applied to flora or soil. The compounds of the invention also contact plants with compositions comprising the compounds of the invention applied as soil drenches of liquid formulations, granular formulations in soil, nursery box treatments or immersion of transplanted plants. It is effectively delivered by plant absorption by. The compound is also effective by topically applying a composition comprising the compound of the present invention to a traverse location. Other methods of contact include direct and residual sprays, air sprays, gels, seed coatings, microencapsulations, total absorption, food, eartags, lumps, atomizers, fumigants, aerosols, fine powders and many Includes application of the compounds or compositions of the invention by others. The compounds of the present invention may also be impregnated into materials for making invertebrate pest control devices (eg, insect net products).

The compounds of the present invention can be incorporated into food consumed by invertebrate pests or in devices such as traps. Granules or foods containing 0.01-5% active ingredient, 0.05-10% water-retaining agent and 40-99% vegetable flour are very low application rates and are especially deadly by oral ingestion rather than direct contact. It is effective in controlling soil insects at the dose of.

The compounds of the invention can be applied in pure form, but in most cases the application is with food, along with suitable carriers, diluents, and surfactants, and perhaps depending on the intended end use. In combination, it may be from a formulation containing one or more compounds. Preferred methods of application include spraying an aqueous dispersion of the compound or a purified oil solution. Combinations with spray oils, spray oil concentrations, sprayer stickers, auxiliaries, other solvents, and synergists such as pyropenylbutoxide often enhance compound efficacy.

The proportion of application required for effective control (ie, "biologically effective amount") is the species of invertent pests to be controlled, the life cycle of the pest, the life stage, its size, location, age. Will depend on factors such as host crop or host animal, feeding behavior, mating behavior, ambient humidity, ambient temperature, etc. Under normal circumstances, a rate of application of about 0.01-2 kg of active ingredient per hectare is sufficient to control pests in the agricultural ecosystem, but as little as 0.0001 kg / hectare may be sufficient, or Large amounts of as much as 8 kg / hectare may be required. For non-agricultural applications, effective usage rates may range from about 1.0 to 50 mg / sqm, but as little as 0.1 mg / sqm may be sufficient, or as much as 150 mg / sqm is required. May be. One of ordinary skill in the art can readily determine the biologically effective amount required to control the desired level of invertebrate pests.

The following tests demonstrate the control efficacy of the compounds of the invention for specific pests. "Control efficacy" refers to inhibition of invertebrate pest growth (including mortality) that causes significantly reduced feeding. However, the pest control protection provided by the compound is not limited to these types. See index tables A through D for compound items. The following abbreviations are used in the following index tables. Me means methyl, Et means ethyl, i-Pr means isopropyl, c-Pr means cyclopropyl, t-Bu means tertiary butyl, Ph means phenyl. .. The abbreviation "Ex." Represents "Example", followed by a number indicating in which example the compound is produced. The abbreviation "dec." Represents "decomposition".

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Biological examples of the present invention Exam A To evaluate the control of diamondback moth (Plutella xylostella), the test unit consisted of a small open container containing a 12-14 day old 20-day radish plant inside. To this, 10 ~ on a small piece of insect diet by using a core sampler to remove the plug from a sheet of hardened insect diet with many larvae growing on it and transfer the plug containing the larvae and diet to the test unit. Fifteen newborn larvae were rampant. The larvae moved onto the test plant as the diet plug was completely dry.

Unless otherwise stated, a 300 ppm X-77® Spreader Lo-Foam Formula containing 10% acetone, 90% water and alkylaryl polyoxyethylene, free fatty acids, glycols and isopropanol. The test compound was formulated using a solution containing a nonionic surfactant (Loveland Industries, Inc.). The compound compound was applied in 1 mL of liquid through a SUJ2 sprayer nozzle on a 1/8 JJ custom body (Spraying Systems Co.) placed 1.27 cm (0.5 inch) above the top surface of each test unit. .. All experimental compounds in this selection were sprayed at 50 ppm and repeated 3 times. Formulation After spraying the test compounds, each test unit was allowed to dry for 1 hour, then a black shielding cap was placed on top. The test unit was kept in the growing room at 25 ° C and 70% relative humidity for 6 days. Next, the damage caused by plant feeding was visually evaluated.

Of the compounds tested, the following gave excellent levels of plant protection (less than 20% feeding damage): 2, 3, 4, 6, 7, 8, 9, 10, 11, 12, 13 , 15, 16, 17, 18, 19, 20, 21, 22, 23, 25, 26, 28, 29, 30, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42 , 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63 and 64.

Exam B To evaluate the control of Spodoptera frugiperda (Spodoptera frugiperda), the test unit consisted of a small open container containing a 4-5 day old corn plant inside. To this, 10 to 15 1-day-old larvae were anteriorly rampant on a small piece of insect diet using a core sampler as described for Test A.

The test compounds were formulated as described for Test A and sprayed at 50 ppm. The application was repeated 3 times. After spraying, the test unit was kept in the growth room and then visually rated as described for Test A.

Of the compounds tested, the following gave excellent levels of plant protection (less than 20% feeding damage): 2, 3, 4, 6, 7, 8, 9, 10, 11, 12, 14 , 15, 16, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63 and 64.

Exam C To evaluate the control of tobacco moth (Heliothis virescens), the test unit consisted of a small open container with a 6-7 day old cotton plant inside. To this, eight 2-day-old larvae were anteriorly rampant on a small piece of insect diet using a core sampler as described for Test A.

The test compounds were formulated as described for Test A and sprayed at 50 ppm. The application was repeated 3 times. After spraying, the test unit was kept in the growth room and then visually rated as described for Test A.

Of the compounds tested, the following gave excellent levels of plant protection (less than 20% feeding damage): 6, 7, 8, 11, 12, 14, 15, 16, 18, 19, 20 , 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46 and 48 ..

Exam D To evaluate the control of beet armyworm (Spodoptera exigua), the test unit consisted of a small open container containing a 4-5 day old corn plant inside. To this, 10 to 15 1-day-old larvae were anteriorly rampant on a small piece of insect diet using a core sampler as described for Test A.

The test compounds were formulated as described for Test A and sprayed at 50 ppm. The application was repeated 3 times. After spraying, the test unit was kept in the growth room and then visually rated as described for Test A.

Of the compounds tested, the following gave excellent levels of plant protection (less than 20% feeding damage): 6, 7, 8, 11, 12, 14, 15, 16, 18, 19, 20 , 21, 22, 23, 24, 25, 28, 29, 30, 32, 34, 41, 42, 43, 44, 45, 46 and 48.

Exam E To evaluate the control of Myzus persicae by contact and / or systemic means, the test unit was internally placed in a small open container containing a 12-15 day old 20 day radish plant. became. To this, 30 to 40 aphids were anteriorly rampant on a piece of leaf excised from the cultured plant by placing it on the leaf of the test plant (cut leaf method). The larvae moved onto the test plant as the leaf pieces dried. After anterior traversal, the soil of the test unit was covered with a layer of sand.

Unless otherwise stated, 300 ppm X-77® Spreader Lo-Foam Formula nonionic containing 10% acetone, 90% water and alkylaryl polyoxyethylene, free fatty acids, glycols and isopropanol. The test compound was formulated using a solution containing a surfactant (Loveland Industries, Inc.). The compound compound was applied in 1 mL of liquid through a SUJ2 sprayer nozzle on a 1/8 JJ custom body (Spraying Systems Co.) placed 1.27 cm (0.5 inch) above the top surface of each test unit. .. All experimental compounds in this selection were sprayed at 250 ppm and repeated 3 times. Formulation After spraying the test compounds, each test unit was allowed to dry for 1 hour, then a black shielding cap was placed on top. The test unit was kept in the growing room at 19-21 ° C and 50-70% relative humidity for 6 days. Next, each test unit was visually evaluated for insect mortality.

Of the compounds tested, the following resulted in at least 80% mortality: 6, 7, 14, 16, 19, 20, 22, 23, 24, 28, 29, 30, 36, 37, 38, 41 , 42, 50, 51, 52, 53, 54, 55, 56, 57, 58, 60 and 61.

Exam F To evaluate the control of cotton melon aphids (Aphis gossypii) by contact and / or systemic means, the test unit consists of a small open container with a 6-7 day old cotton plant inside. It was. To this, 30-40 aphids were anteriorly rampant on a leaf piece according to the cut leaf method described for Test E, and the soil of the test unit was covered with a layer of sand.

The test compounds were formulated as described for Test E and sprayed at 250 ppm. The application was repeated 3 times. After spraying, the test unit was retained in the growth chamber and then visually rated as described for Test E.

Of the compounds tested, the following resulted in at least 80% mortality: 19, 20, 24, 36, 37, 38, 39, 40, 42, 50, 51, 54, 56, 57, 58 and 61: ..

Exam G To evaluate the control of corn planthoppers (Peregrinus maidis) by contact and / or systemic means, the test unit is a small open container with a 3-4 day old corn plant (ear) inside. Prior to application, white sand was added to the top surface of the soil. The test compound was formulated as described for Test E and sprayed at 250 ppm and repeated 3 times. After spraying, the test unit 10-20 corn planthoppers (18-20 day old larvae) were anteriorly rampant by leaving them to dry for 1 hour and then sprinkling them on the sand with a salt shaker. A black shielding cap was placed on top of the cylinder. The test units were kept in the growing room at 19-21 ° C and 50-70% relative humidity for 6 days. Then each test unit was visually evaluated for insect mortality.

Of the compounds tested, the following resulted in at least 80% mortality: 14, 36, 37, 40 and 56.

Test H To evaluate the control of potato leafhoppers (Empoasca fabae Harris) by contact and / or systemic means, the test unit was internally 5-6 days old Longio legumes ( It consisted of a small open container containing (primary leaf appearance). White sand was added to the top surface of the soil and one of the primary leaves was excised prior to application. The test compound was formulated as described for Test E, sprayed at 250 ppm and repeated 3 times. After spraying, the test unit was allowed to dry for 1 hour, after which 5 potato leafhoppers (18-21 day old adults) were anteriorly rampant. A black shielding cap was placed on top of the cylinder. The test unit was kept in the growing room at 19-21 ° C and 50-70% relative humidity for 6 days. Each test unit was then visually evaluated for insect mortality.

Of the compounds tested, the following resulted in at least 80% mortality: 17, 19, 35, 48, 50, 51, 52, 53, 54, 55, 56, 57, 58 and 59. The main features and aspects of the present invention can be summarized as follows. 1. Equation I<chemistry num="41"><img file="JP4224397B2_D0094.tif" /></chemistry>(During the ceremony, A and B are independently O or S, X is N or CR¹⁰And Y is N or CH, R¹Is H; R¹¹; Or each, in some cases R⁶, Halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino, (C₁-C₄Alkyl) C₃-C₆Cycloalkylamino and R¹¹May be substituted with one or more substituents selected from the group consisting of C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne or C₃-C₆Cycloalkyl, R²Is H, C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne, C₃-C₆Cycloalkyl, C₁-C₄Alkoxy, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino, (C₁-C₄Alkyl) C₃-C₆Cycloalkylamino, C₂-C₆Alkoxycarbonyl or C₂-C₆Alkylcarbonyl, R³Is H; R¹¹; Or each, in some cases R⁶, Halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₃-C₆Trialkylsilyl, R¹¹, Each phenyl, phenoxy and 5- or 6-membered aromatic heterocycle may be optionally substituted with 1-3 substituents selected independently of W and optionally 1 R¹²May be substituted with one or more substituents selected from the group consisting of phenyl, phenoxy and 5- or 6-membered aromatic heterocycles optionally substituted with C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne or C₃-C₆Cycloalkyl or R²And R³Can form K together with the nitrogen they are bound to, R⁴Is C₁-C₄Alkyl, C₁-C₄Haloalkyl, CN, halogen, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄It is a haloalkyl sulfonyl and R⁵And R⁸Are independent of each other, H; C₁-C₄Alkyl; C₁-C₄Halogen; Halogen; R¹²; G; J; OJ; OG; S (O)_p-J; S (O)_p-G; In some cases, it may be substituted with 1 to 3 substituents selected independently of W, and in some cases, 1 R.¹²May be replaced by S (O)_p-Phenyl; G, J, R respectively⁶, Halogen, CN, NO₂, NH₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄Haloalkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆The trialkylsilyl, each phenyl and phenoxy ring may be optionally substituted with 1 to 3 substituents selected independently of W and optionally 1 R.¹²C substituted with one or more substituents selected from the group consisting of a phenyl ring and a phenoxy ring optionally substituted with₁-C₁₀Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne, C₁-C₄Alkoxy or C₁-C₄Alkylthio Each G is independently C (= O), SO or S (O)₂Arbitrarily contains one or two ring elements selected from the group consisting of and optionally C₁-C₂Alkyl, halogen, CN, NO₂And C₁-C₂It is a 5- or 6-membered non-aromatic heterocyclic ring that may be substituted with 1 to 4 substituents selected from the group consisting of alkoxy, or Each G is C independently₂-C₆Alkenyl, C₂-C₆Alkyne, each cycloalkyl, (alkyl) cycloalkyl and (cycloalkyl) alkyl may optionally be substituted with one or more halogens C₃-C₇Cycloalkyl, (cyano) C₃-C₇Cycloalkyl, (C₁-C₄Alkyl) C₃-C₆Cycloalkyl, (C₃-C₆Cycloalkyl) C₁-C₄Alkyl Each J may be substituted with 1 to 3 substituents, optionally selected independently of W, and optionally R.¹²A 5- or 6-membered aromatic heterocycle optionally substituted with, Each R⁶Independently R¹⁹C (= E)-, R¹⁹C (= E) L-, R¹⁹LC (= E)-, (R¹⁹) LC (= E) L-, -O (Q =) P (OR)¹⁹)₂, -SO₂LR¹⁸, Or R¹⁹SO₂L- Each E is independently O, S, NR¹⁵, NOR¹⁵, NN (R¹⁵)₂, NS = O, N-CN or N-NO₂And R⁷Is H, C₁-C₄Alkyl, C₁-C₄Haloalkyl, halogen, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄It is a haloalkyl sulfonyl and R⁹Is CF₃, OCF₃, OCHF₂, OCH₂CF₃, S (O)_pCF₃, S (O)_pCHF₂Or halogen, R¹⁰Is H, C₁-C₄Alkyl, C₁-C₄Haloalkyl, halogen, CN or C₁-C₄It is haloalkoxy and Each R¹¹Independently C₁-C₆Alkylthio; C₁-C₆Alkyl sulphenyl; C₁-C₆Haloalkylthio; C₁-C₆Haloalkyl sulphenyl; phenylthio or phenylsulphenyl, respectively, optionally substituted with 1 to 3 substituents selected independently of W; (R)¹⁶)₂NS (O)_n-; R¹³C (= O)-; R¹⁴C (= O) L-; R¹⁴LC (= O) S-; R¹³LC (= O)-; R¹³C (= O) NR¹³S (O)_n-; R¹⁴LC (= O) NR¹³S (O)_n-Or R¹⁴LSO₂NR¹³S (O)_n-And Each L is independently O, NR¹⁸Or S Each R¹²Independently B (OR¹⁷)₂, NH₂, SH, Thiosianato, C₃-C₈Trialkylsilyloxy, C₁-C₄Alkyl disulfide, SF₅, R¹⁹C (= E)-, R¹⁹C (= E) L-, R¹⁹LC (= E)-, (R¹⁹) LC (= E) L-, -OP (= Q) (OR¹⁹)₂, -SO₂LR¹⁹, R¹⁹SO₂L- Q is O or S Each R¹³Independently hydrogen; each, in some cases R⁶, Halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino and (C₁-C₄Alkyl) C₃-C₆C may be substituted with one or more substituents selected from the group consisting of cycloalkylaminos₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne or C₃-C₆Cycloalkyl, Each R¹⁴Are, in some cases, R⁶, Halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino and (C₁-C₄Alkyl) C₃-C₆C may be substituted with one or more substituents selected from the group consisting of cycloalkylaminos₁-C₂₀Alkyl, C₂-C₂₀Alkenyl, C₂-C₂₀Alkyne or C₃-C₆Cycloalkyl; or optionally substituted with 1-3 substituents selected independently of W and optionally R¹²Phenyl which may be substituted with Each R¹⁵Independently H; C₁-C₆Haloalkyl; possibly CN, NO₂, R⁶, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄Haloalkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylcarbonyl, C₃-C₆It may be substituted with trialkylsilyl, and optionally 1 to 3 substituents selected independently of W, and optionally 1 R.¹²May be substituted with one or more substituents selected from the group consisting of phenyl rings optionally substituted with C₁-C₆Alkyl; or optionally substituted with 1-3 substituents selected independently of W and optionally R¹²Phenyl which may be substituted with N (R¹⁵)₂Can form K together, R¹⁶Is C₁-C₁₂Alkyl or C₁-C₁₂Haloalkyl or N (R¹⁶)₂Can form K together, Each R¹⁷Is independently H or C₁-C₄Alkyl or B (OR¹⁷)₂May be methyl or C₂-C₆A chain of two to three carbon atoms, which may be substituted with one or two substituents selected independently of the alkoxycarbonyl, can form a ring in which two oxygen atoms are linked. Each R¹⁸Are independently H, C₁-C₆Alkyl or C₁-C₆Haloalkyl or N (R¹³) (R¹⁸) Can form K together, Each R¹⁹Independently H; in some cases CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl, C₁-C₄Haloalkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, CO₂H, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylcarbonyl, C₃-C₆Substituent with one or more substituents selected from the group consisting of trialkylsilyls and optionally 1 to 3 substituents selected independently of W and optionally a phenyl ring. May be C₁-C₆Alkyl; C₁-C₆Haloalkyl; C₃-C₆Cycloalkyl; or phenyl or pyridinyl, optionally substituted with 1 to 3 substituents selected independently of W. Each K is a substituent pair R¹³And R¹⁸, (R¹⁵)₂Or (R¹⁶)₂Is a ring that may contain 2 to 6 carbon atoms and optionally an additional nitrogen, sulfur or oxygen atom in addition to the nitrogen atom to which the ring is attached, which ring is optionally C.₁-C₂Alkyl, halogen, CN, NO₂And C₁-C₂It may be substituted with 1 to 4 substituents selected from the group consisting of alkoxy. Each W is C independently₁-C₄Alkyl, C₂-C₄Alkenyl, C₂-C₄Alkyne, C₃-C₆Cycloalkyl, C₁-C₄Haloalkyl, C₂-C₄Haloalkenyl, C₂-C₄Halo alkynyl, C₃-C₆Halocycloalkyl, halogen, CN, NO₂, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino, C₃-C₆Cycloalkylamino, (C₁-C₄Alkyl) C₃-C₆Cycloalkylamino, C₂-C₄Alkylcarbonyl, C₂-C₆Alkoxycarbonyl, CO₂H, C₂-C₆Alkylaminocarbonyl, C₃-C₈Dialkylaminocarbonyl or C₃-C₆Trialkylsilyl, Each n is 0 or 1 independently, and Each p is 0, 1 or 2 independently, However, (a) R⁵Is H, C₁-C₆Alkyl, C₁-C₆Haloalkyl, C₂-C₆Haloalkenyl, C₂-C₆Halo alkynyl, C₁-C₄Haloalkoxy, C₁-C₄Haloalkylthio or halogen and (b) R⁸Is H, C₁-C₆Alkyl, C₁-C₆Haloalkyl, C₂-C₆Haloalkenyl, C₂-C₆Halo alkynyl, C₁-C₄Haloalkoxy, C₁-C₄Haloalkylthio, halogen, C₂-C₄Alkylcarbonyl, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylaminocarbonyl or C₃-C₈In the case of dialkylaminocarbonyl, (c) R⁶, R¹¹And R¹²There is at least one substituent selected from the group consisting of, and (d) R¹²If does not exist, then R⁶Or R¹¹At least one of₂-C₆Alkylcarbonyl, C₂-C₆Alkoxycarbonyl, C₂-C₆Alkylaminocarbonyl and C₃-C₈Other than dialkylaminocarbonyl) Compounds and their N-oxides and salts. 2. Both A and B are O J may be substituted with 1 to 3 substituents in which each J ring is optionally selected independently of W and optionally R.¹²A 5- or 6-membered aromatic heterocycle selected from the group consisting of J-1, J-2, J-3 and J-4 which may be substituted with.<chemistry num="42"><img file="JP4224397B2_D0095.tif" /></chemistry> Q¹Is O, S or NW, and W¹, X¹, Y¹And Z¹Is independently N or CW, but in J-3 and J-4 W¹, X¹, Y¹Or Z¹The compound according to 1 above, wherein at least one of the compounds is N. 3. R⁶, R¹¹And R¹²The compound according to 2 above, wherein there is one substituent substituted from the group consisting of. 4. Equation Is<chemistry num="43"><img file="JP4224397B2_D0096.tif" /></chemistry>(During the ceremony, X is N or CR¹⁰And Y is N or CH, R¹Is H, or R¹¹And R²Is C₁-C₆Alkyl R³Is H, or R¹¹And R⁴Is C₁-C₄Alkyl or halogen, R⁵Is H, C₁-C₄Alkyl, C₁-C₄Halogen or halogen, R⁷Is C₁-C₄Halogen or halogen, R⁸Is H R⁹Is CF₃, OCF₃, OCHF₂, OCH₂CF₃, S (O)_pCF₃, S (O)_pCHF₂Or halogen, Each R¹¹Independently C₁-C₆Alkylthio; C₁-C₆Haloalkylthio; optionally substituted with 1 to 3 substituents selected independently of W; SN (R)¹⁶)₂; R¹⁴C (= O) L¹-; R¹⁴L²C (= O) S-; R¹⁴L²C (= O) NR¹³S- or R¹⁴SO₂NR¹³S- L¹Is NR¹³Or S Each L²Independently O, NR¹³Or S Each R¹³Independently hydrogen; optionally halogen, CN, NO₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino and C₃-C₆C may be substituted with one or more substituents selected from the group consisting of cycloalkylaminos₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne or C₃-C₆Cycloalkyl, Each R¹⁴Halogen, CN, NO, respectively₂, Hydroxy, C₁-C₄Alkoxy, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Alkylamino, C₂-C₈Dialkylamino and C₃-C₆C may be substituted with one or more substituents selected from the group consisting of cycloalkylaminos₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkyne or C₃-C₆Cycloalkyl; or phenyl optionally substituted with 1 to 3 substituents selected independently of W, and R¹⁶Is C₁-C₄Alkyl or C₁-C₄Haloalkyl or N (R¹⁶)₂Can together form a ring that may contain a nitrogen atom, 2-6 carbon atoms and optionally one additional atom of nitrogen, sulfur or oxygen, which ring may optionally. C₁~ C₂Alkyl, halogen, CN, NO₂And C₁-C₂It may be substituted with 1 to 4 substituents selected from the group consisting of alkoxy. However, one R¹¹Exists) The compound according to 3 above. 5. X is N and Y is N, R⁴Is CH₃, F, Cl or Br, R⁵Is H, CF₃, F, Cl, Br or I, R⁷Is Cl or Br, and R⁹Is CF₃, OCHF₂, OCH₂CF₃, Cl or Br The compound according to 4 above. 6. R¹Is H, R²Is H or C₁-C₆Alkyl R³Is C₁-C₆Alkyl R⁵Is CN, NO₂, NH₂, Hydroxy and R₆C substituted with one substituent selected from the group consisting of₁-C₁₀Alkyl, or R¹²And R⁶Is R¹⁹C (= E)-, R¹⁹C (= E) L-, R¹⁹LC (= E)-or (R¹⁹) LC (= E) L-, R¹²Is NH₂, R¹⁹C (= E)-, R¹⁹C (= E) L-, R¹⁹LC (= E)-or (R¹⁹) LC (= E) L-, Each E is independently O or NOR¹⁵And Each L is independently O or NR¹⁸And Each R¹⁵Is independently H or C₁-C₄Alkyl and Each R¹⁸H, C independently₁-C₆Alkyl or C₁-C₆Haloalkyl The compound according to 3 above. 7. R⁵Is R¹²And R¹²Is NH₂, R¹⁹C (= O) L- or (R¹⁹) LC (= O) L-, Each L is independently NR¹⁸And then Each R¹⁸H, C independently₁-C₆Alkyl or C₁-C₆Haloalkyl The compound according to 6 above. 8. R⁵C substituted with hydroxy₁-C₁₀Alkyl, or R¹²And R¹²Is R¹⁹C (= E)-or (R¹⁹) LC (= O)-and E is O or NOR¹⁵And L is O or NR¹⁸And R¹⁵Is H or C₁-C₄Alkyl and R¹⁸Is H, C₁-C₆Alkyl or C₁-C₆Haloalkyl The compound according to 6 above. 9. R¹Is H, R²Is H or C₁-C₆Alkyl R³Is C₁-C₆Alkyl R⁵Is H, C₁-C₄Alkyl, C₁-C₄Halogen or halogen, R⁸Is CN, NO₂, NH₂, Hydroxy and R₆C substituted with one substituent substituted from the group consisting of₁-C₁₀Alkyl, or R¹²And R⁶Is R¹⁹C (= E)-, R¹⁹C (= E) L-, R¹⁹LC (= E)-or (R¹⁹) LC (= E) L-, R¹²Is R¹⁹C (= E¹)-, R¹⁹C (= E²) L-, R¹⁹LC (= E)¹)-Or (R¹⁹) LC (= E²) L- Each E is independently O or NOR¹⁵And Each E¹Is NOR¹⁵And Each E²Is independently O or NOR¹⁵And Each L is independently O or NR¹⁸And Each R¹⁵Is independently H or C₁-C₄Alkyl Each R¹⁸H, C independently₁-C₆Alkyl or C_1f-C₆Haloalkyl and Each R¹⁹H, C independently₁-C₆Alkyl, C₁-C₆Haloalkyl, C₃-C₆Cycloalkyl, or phenyl optionally substituted with 1 to 3 substituents selected independently of W, The compound according to 3 above. 10. R⁸Is NH₂, Hydroxy and R⁶C substituted with one substituent selected from the group consisting of₁-C₁₀Alkyl, or R¹²And R⁶Is R¹⁹C (= O) L-, R¹²Is R¹⁹LC (= O)-and Each L is independently NR¹⁸Is, The compound according to 9 above. 11. 1- [2- (Hydroxymethyl) phenyl] -N- (2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl) -3- (trifluoromethyl) -1H-pyrazol- 5. The compound according to 10 above, which is 5-carboxamide. 12. R¹Is H, R²Is H or C₁-C₆Alkyl R³Is one R⁶C replaced by₁-C₆Alkyl R⁴Is C₁-C₄Alkyl or halogen, R⁵Is H, C₁-C₄Alkyl, C₁-C₄Halogen or halogen, R⁶Is R¹⁹C (= E¹)-, R¹⁹C (= E²) L-, R¹⁹LC (= E)¹)-Or (R¹⁹) LC (= E²) L- Each E¹Independently S, NR¹⁵, NOR¹⁵, NN (R¹⁵)₂And Each E²Independently O, S, NR¹⁵, NOR¹⁵, NN (R¹⁵)₂And Each L is independently O or NR¹⁸And R⁷Is C₁-C₄Halogen or halogen, R⁸Is hydrogen, R⁹Is CF₃, OCF₃, OCHF₂, OCH₂CF₃, S (O)_pCF₃, S (O)_pCHF₂Or halogen, Each R¹⁵Independently H; C₁-C₆Haloalkyl; possibly CN, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkyl sulfinyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylthio, C₁-C₄Haloalkylsulfinyl and C₁-C₄C may be substituted with one substituent selected from the group consisting of haloalkylsulfonyls₁-C₆Alkyl Each R¹⁹Is independently H or C₁-C₆Alkyl and Each p is 0, 1 or 2 independently, The compound according to 3 above. 13. R³Is one R⁶C replaced by₁-C₆Alkyl R⁶Is R¹⁹C (= E¹)-And E¹Is NOR¹⁵Is, The compound according to 12 above. 14. R⁵Is NH₂The compound according to 1 above. 15. N- [4-Amino-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl)- The compound according to claim 14, which is 1H-pyrazole-5-carboxamide. 16. 4-[[[[1- (3-Chloro-2-pyridinyl) -3- (trifluoromethyl) -1H-pyrazol-5-yl] carbonyl] amino] -3-methyl-5-[[(1) -Methylethyl) amino] carbonyl] methyl benzoate, N- [4-Acetyl-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H- Pyrazole-5-carboxamide, and N- [4-benzoylamino-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -1- (3-chloro-2-pyridinyl) -3- (trifluoromethyl) -1H -Pyrazole-5-carboxamide The compound according to 1 above, which is selected from the group consisting of. 17. 17. Control of invertebrate pests comprising contacting an invertebrate pest or its environment with a biologically effective amount of the compound according to 1 above, its N-oxide or a suitable salt thereof. Method. 18. The method according to 17 above, comprising applying a composition comprising the compound and at least one additional compound or agent for the control of a biologically effective amount of invertebrate pests. .. 19. A biologically effective amount of the compound according to claim 1, as well as At least one selected from the group consisting of surfactants, solid diluents and liquid diluents A composition for controlling invertebrate pests containing additional constituents. 20. The composition according to 19 above, further comprising at least one additional compound or agent for the control of invertebrate pests.