KR19990077277A - Oxazoline living arthropods - Google Patents

Abstract

0.0 > (I) < / RTI > of the formula (I) and its pharmaceutically acceptable salts which are useful as diuretic agents. Also disclosed are compositions comprising a compound of formula I and an arthropod control method comprising contacting an arthropod or an environment thereof with an effective amount of a compound of formula I.

(I)

Wherein,

R ¹ - R ⁵ and n are as defined above.

Description

Oxazoline living arthropods

The present invention relates to certain oxazolines, their agriculturally suitable salts and compositions, and their use as aged animals in agricultural and non-agricultural environments.

Control of arthropod pests is very important for obtaining crops in high yield. Damage to arthropods on growing and stored agricultural crops significantly reduces productivity and increases consumer purchasing costs. Control of arthropod pests in forestry, greenhouse crops, corn crops, seedbed crops, preserved food and textile products, livestock, families and public and animal hygiene is also important. While a number of products for this purpose are commercially available, there is a continuing need for new compounds that are more effective, cheaper, environmentally safe, less toxic, or have a variety of activity types.

WO 95/04726 discloses compounds of the general formula (i) as follows:

(i)

Wherein,

A is selected from the group of direct bonds and C ₁ -C ₃ straight chain or branched alkylene;

E is selected from the group of C ₁ -C ₄ alkyl and C ₁ -C ₄ haloalkyl;

Z is selected from the group of O and S;

R ¹ and R ² are independently selected from the group of H, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, CN and NO ₂ Is selected.

The compounds of the present invention are unexpectedly more effective, environmentally safe and less toxic than the compounds described in WO 95/04726.

SUMMARY OF THE INVENTION

The present invention relates to compounds of formula (I), including all geometric and stereoisomeric forms thereof, to agriculturally suitable salts thereof, to agricultural compositions comprising them, and to their use as an insecticidal agent.

Wherein,

R < ¹ > is H, F or Cl;

R ² is F or Cl;

R < ³ > is H or F;

R ⁴ is C ₁ -C ₂ haloalkyl;

R ⁵ is H, F, Cl, C ₁ -C ₂ alkyl, or C ₁ -C ₂ alkoxy;

n is 0, 1 or 2;

With the proviso that when i) R ² is F, R ³ and R ⁵ are H and n is 0, R ⁴ is other than CF ₃ ;

ii) when R ¹ is F, R ² is Cl, R ³ and R ⁵ are H, and n is 0, then R ⁴ is other than CF ₃ .

Among the above descriptions, the term " alkyl " used alone or in compound terms such as " haloalkyl " includes methyl and ethyl. &Quot; Alkoxy " includes methoxy and ethoxy.

The term " halogen ", used alone or in compound term such as " haloalkyl " includes fluorine, chlorine, bromine or iodine. Further, when used in a compound term such as " haloalkyl ", the alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of " haloalkyl " are F ₃ C, ClCH ₂ , CF ₃ CH ₂ and CF ₃ CCl ₂ .

The total number of substituents of the carbon atoms has a prefix "C _i -C _j" is represented by (wherein, i and j is the number of 1 to 2). For example, C ₁ -C ₂ alkyl represents methyl and ethyl, and C ₁ -C ₂ alkoxy represents CH ₃ O and CH ₃ OCH ₂ O.

When a group includes a substituent which may be hydrogen, for example, R ¹ or R ⁵ , and these substituents are hydrogen, it is understood that this group is the same as the one in which the group is not substituted.

The compounds of the present invention may exist in one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, rotational isomers and geometric isomers. One of ordinary skill in the art will appreciate that when one stereoisomer is separated from more or different stereoisomers than the other stereoisomers, the stereoisomers may exhibit more active and / or beneficial effects. In addition, those skilled in the art are aware of how to separate, increase, and / or selectively produce the stereoisomers. Accordingly, the present invention includes compounds selected from Formula I and an agriculturally suitable salt thereof. The compounds of the present invention may exist in a mixture of stereoisomers, in their respective stereoisomers, or in an optically active form.

Examples of salts of the compounds of the present invention include salts with inorganic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, Or acid addition salts with inorganic or organic acids such as valeric acid. The salt of the compound of the present invention may also be a salt of the compound of the present invention such as an organic base (e.g., pyridine, ammonia, or triethylamine) or an inorganic base (e.g., sodium, potassium, lithium, calcium , Hydrides of magnesium or barium, hydroxides, or carbonates).

Preferred compounds in terms of better activity, environmental safety, less toxicity and / or easier synthesis are as follows.

Preferred compounds 1): Among the compounds of formula I above,

R ¹ and R ² are F;

R ³ is H;

R ⁴ is CF ₂ H, CF ₃ , CF ₂ Br, CF ₂ CF ₂ H or CF ₂ CF ₃ , and an agriculturally suitable salt thereof.

Preferred compounds 2): Among the compounds of formula I above,

R ¹ , R ² and R ³ are F;

R ⁴ is CF ₂ H, CF ₃ , CF ₂ Br, CF ₂ CF ₂ H or CF ₂ CF ₃ , and an agriculturally suitable salt thereof.

Preferred compounds 3): Among the compounds of formula I above,

R < ¹ > is F;

R ² is Cl;

R < ⁵ > is H, and an agriculturally suitable salt thereof.

The most preferred compounds are selected from the following group among the compounds of the preferred compounds 3:

2- (2-Chlorophenyl) -4- [4 '- [(difluoromethyl) thio] [1,1'-biphenyl] -4-yl] -4,5-dihydrooxazole;

2- (2-Chlorophenyl) -4- [4 '- [(difluoromethyl) sulfinyl] [1,1'-biphenyl] -4-yl] -4,5-dihydrooxazole; And

2- (2-Chlorophenyl) -4- [4 '- [(difluoromethyl) sulfonyl] [1,1'-biphenyl] -4-yl] -4,5-dihydrooxazole.

Preferred compounds 4) Among the preferred compounds 1,

R < ⁵ > is H.

Preferred compounds 5) Among the preferred compounds 4,

The compound R ⁴ is CF ₂ H, CF ₃ or CF ₂ Br.

The most preferred compounds are selected from the following group among the preferred compounds of compound 5:

4- [4 '- [(difluoromethyl) thio] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) -4,5-dihydrooxa Sol;

4- [4 '- [(difluoromethyl) sulfinyl] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) -4,5- Oxazole;

4- [4 '- [(difluoromethyl) sulfonyl] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) -4,5- Oxazole;

Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- - dihydrooxazole;

Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- S-type sulfoxide of dihydrooxazole;

Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- R-form sulfoxide of dihydrooxazole;

Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- - Sulfones of dihydrooxazole.

The present invention also relates to a flesh odoriferous composition consisting of at least one of a compound of formula I and a surfactant, solid diluent or liquid diluent. Preferred compositions of the present invention include those preferred compounds.

The present invention also relates to a method of controlling arthropod comprising contacting an arthropod or an environment thereof with an arthritically effective amount of a compound of formula (I), for example a composition as described herein. A preferred method of use is a method using the above-mentioned preferred compounds.

Compounds of formula I may be prepared by one or more of the methods and variations described in the following Schemes 1-3. The definitions of R ¹ -R ⁵ and n in the compounds of formulas I-VII are as defined in the Summary of the Invention above.

(I)

The compounds of formula (I) used as active ingredients in the present invention can be prepared, for example, by the steps shown in the following scheme using compounds of formula (II). The compound of formula II, wherein R ¹ is F, R ² is F, R ³ is H, R ⁵ is H, and R ²⁰ is I, 2- (2,6 -Difluorophenyl) -4,5-dihydro-4- (4-iodophenyl) oxazole) can be prepared by the method described in WO 95/04726. The reaction of Scheme 1 can be carried out at a temperature of the boiling point of an inert solvent selected from -78 ° C to tetrahydrofuran (THF), ethyl ether, hexane, toluene and the like for 30 minutes to 72 hours in the presence of a transition metal catalyst, (II) chloride, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) chloride or palladium (II) For example tri-ortho-tolylphosphine or triphenylarsine and is carried out in the presence or absence of additional auxiliary components such as lithium chloride, copper (I) iodide, or dialkyl- or trialkylamine 0.0 > IV < / RTI >

Wherein,

R ⁶ = R ⁴ or a protecting group,

And the like ^{R 20 = I, Br, OSO} 2 CF 3, OSO 2 F,

Met = the MgX, ZnX (X = Cl, Br, I), SnMe 3, SnBu 3, B (OH) 2 and the like.

Intermediates of formula (III) are prepared by procedures known in the art. R ⁶ can be the same as R ⁴ , in which case the compound of formula I can be prepared directly. Or for easy synthesis, R < ⁶ > may be a sulfur-protecting group such as, for example, t-butyldimethylsilyl, t-butyl, p-methoxybenzyl and the like.

When R < ⁶ > is a protecting group, the compound of formula (I) may be prepared by deprotection of the sulfur and further reaction as shown in Scheme 2. The reaction of the intermediate of formula V is carried out in any inert solvent selected from tetrahydrofuran (THF), dioxane, ethyl ether, dichloromethane, hexane, toluene and the like for 5 minutes to 72 hours, Lt; / RTI > Optionally in the presence of a phase transfer catalyst, with a base such as sodium hydroxide, potassium hydroxide, potassium t-butoxide or the like in the presence of a hydrohalocarbon such as chlorodifluoromethane, chloroform or the like, or optionally in the presence of a base, Substituted with a leaving group such as iodide, bromide, chloride, methanesulfonate, p-toluenesulfonate or the like in the presence of sodium hydride, sodium hydroxide, potassium hydroxide, potassium t-butoxide or the like and optionally in the presence of a phase transfer catalyst Hydrohalo-or halocarbons provide compounds of formula (I). Alternatively, the compound of formula (V) can be reacted with an activated alkene, such as tetrafluoroethylene, in the presence of any basic, acidic or radical catalyst. Alternatively, mercaptans of formula V can be oxidized to the disulfide (see p. 1092, Advanced Organic Chemistry, 3rd edition, J. March, (1985), John Wiley & Sons, , Can be converted to compounds of formula I by reaction with halogenoalkanes and radical initiators (see, for example, C. Wakselman et al., J. Chem. Soc., Chem. Commun., (1991), 993) ).

Wherein,

X = F, Cl, Br, I (mixable)

Y = Cl, Br, I,

PTC = phase transfer catalyst, for example BnEt ₃ N ⁺ or Bu ₄ N ⁺ salt,

L = Leakage period (see text).

Compounds of formula (I) are also prepared as in scheme (3). Compounds of formula II can be prepared by reacting a metal complex such as tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) chloride or, for example, tri-ortho-tolylphosphine or (I) iodide, dialkyl- or trialkylamine and the like under catalysis with palladium (II) acetate in the presence of an auxiliary auxiliary component such as lithium chloride, copper For example, by reaction with a hexamethyl dialkyl tin. Then, a tin-based derivative of Formula VI is reacted with a substituted aromatic derivative of Formula VII in the presence of a metal complex having the catalytic action described above, the compound of the compound of formula IV, i.e., R ⁶ = R ⁴ of the formula I Or, if R < ⁶ > is a protecting group, can then be converted to a compound of formula I by the chemical reaction of Scheme 2.

Wherein,

R ⁶ = R ⁴ or a protecting group,

R < ²⁰ > = as defined in Scheme 1,

R ²¹ is independently the same as defined for R ²⁰ ,

n = 0, 1, 2.

Compounds of formula (I) wherein n = 1 or 2 are prepared from compounds of formula I wherein n = 0 by the action of mild oxidizing agents such as organic peracids, sodium periodate (see, for example, March, pp. 1089-1090, etc.). Alternatively, a product of formula (I) wherein n = 1 or 2 is obtained by a chemical reaction of scheme 3, using an intermediate such as a compound of formula VII, for example n = 1 or 2.

The desired product can be prepared by conventional post-reaction procedures such as extraction, filtration, and concentration and, if necessary, can be suitably further purified by methods such as chromatography and / or crystallization.

It is believed that some of the reagents and reaction conditions described above for preparing compounds of formula (I) may not be compatible with the particular functionality exhibited by the intermediates. In such a case, a continuous process of protection / deprotection or a mutual change of the functional groups during the synthesis may be included to facilitate obtaining the desired product. The use and selection of protecting groups will be apparent to those skilled in the art of chemical synthesis (see, for example, Greene, T. W., Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed .; Wiley; New York, 1991). It will be appreciated by those skilled in the art that, in order to complete the synthesis of the compounds of formula I, it is necessary in some cases to introduce a given reagent as shown in any of the individual reaction schemes, followed by further general synthetic procedures not shown in detail .

It will also be appreciated by those skilled in the art that the compounds of formula I and intermediates described herein may be subjected to various electrophilic, nucleophilic, radial, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents .

Without further elaboration, it is believed that one skilled in the art can, using the preceding detailed description, utilize the present invention to its fullest extent. In other words, the following embodiments are only for explanation of the disclosure. Percentages are by weight, unless otherwise noted or a mixture of chromatographic solvents. Unless otherwise stated, parts and percentages of the chromatographic solvent mixture are on a volume basis. ^& Lt; ¹ > H NMR spectra are recorded downfield from ppm of tetramethylsilane; m = polyline.

Example 1

Step A: Preparation of [(4-bromophenyl) thio] tris (1-methylethyl) silane

Under a nitrogen atmosphere, to a solution of 45 g of 4-bromothiophenol in 250 mL of THF was added 53 mL of triisopropylsilyl chloride and 38 mL of DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) . The reaction mixture was spontaneously heated to reflux. The reaction mixture was cooled and diluted with 500 mL of hexane. The resulting white suspension was filtered through Celite (diatomaceous earth) pad and the filter cake was washed with additional 100 mL of hexane and ether. The filtrate was washed with 0.1 N HCl ice-cooled aqueous solution, water, NaHCO₃Aqueous solution, and a saturated aqueous NaCl solution, and dried over MgSO4₄ ≪ / RTI > and concentrated in vacuo to give 82 g of the title compound as a clear oil phase, step A,^One1 H NMR (CDCl 3₃, 300 MHz) [delta] 1.1 (m, 18H), 1.2 (m, 3H), 7.3-7.4 (m, 4H).

Step B: Preparation of 2- (2,6-difluorophenyl) -4,5-dihydro-4- [4 '- [[tris (1- methylethyl) silyl] thio] [1,1'- ] -4-yl] oxazole

The title compound of Step A (4.3 g) was dissolved in 15 mL of THF under a nitrogen atmosphere and the reaction mixture was cooled to below -65 C and then 4.7 mL of 2.5 M n-BuLi / hexane solution was added dropwise. After 15 minutes, 26 mL of 0.5 M ZnCl ₂ / THF solution was added dropwise. In a separate reaction flask, 67 mg of Pd (OAc) ₂ are added to a solution of tri (o-tolyl) phosphine in 201 mg of THF in 5 mL, the mixture is stirred for 5 minutes and then added to the main reaction mixture via a cannula Respectively. (2,6-difluorophenyl) -4,5-dihydro-4- (4-iodophenyl) oxazole (prepared as described in WO 95/04726) in 10 mL of THF was treated with , And the reaction mixture was warmed to room temperature and stirred for 2 to 3 hours. The reaction mixture was poured into an ice cold aqueous solution of NH ₄ Cl and extracted with ethyl acetate. The organic phase was washed with saturated aqueous NaCl, dried over MgSO _4, and concentrated in vacuo. The oily residue was adsorbed onto silica gel, loaded onto a silica gel column and eluted with hexane / ethyl acetate (6: 1 v: v) to give the title compound as a viscous oil phase, step B, 3.6 g. _{^{1 H NMR (CDCl 3, 300}} MHz): δ 1.1 (m, 18H), 1.3 (m, 3H), 4.3 (m, 1H), 4.8 (m, 1H), 5.5 (m, 1H), 7.0 (m , 2H) 7.3-7.4 (m, 5H), 7.5-7.6 (m, 4H).

Step C: 4- [4 '- [(difluoromethyl) thio] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) Preparation of dihydrooxazole

To a solution of 10.9 g of the title compound of Step B in 20 mL of THF was added 23 mL of n-Bu ₄ NF 1.0 M commercial solution in THF (containing 5% water) at 15-20 ° C (bath cooling) under a nitrogen atmosphere. After 5 minutes, freshly pulverized KOH (5.9 g) was added followed by an excess of Freon (TM) 22 (chlorodifluoromethane) at a rate sufficient to maintain a slight overpressure Respectively. After 20-30 minutes, the gas addition was stopped and the reaction mixture was poured into an ice cold aqueous solution of NH ₄ Cl and extracted with ethyl acetate. The organic phase was washed with water and saturated aqueous NaCl, dried over MgSO _4, and concentrated in vacuo. The residue was adsorbed onto silica gel, loaded onto a silica gel column and eluted with hexane / ethyl acetate (4: 1 to 3: 1 v: v) to give an oil. Trituration with ether and hexane gave an oil which crystallized to yield a white solid which was dried to yield 6.2 g of the title compound of the invention, step C, melting point 72-76 캜. _{^{1 H NMR (CDCl 3, 300}} MHz): δ 4.3 - 4.4 (m, 1H), 4.8 (m, 1H), 5.5 (m, 1H), 6.85 (m, 1H), 7.0 (m, 2H), 7.4 - < / RTI > 7.7 (m, 9H).

Example 2

4- [4 '- [(difluoromethyl) thio] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) -4,5-dihydrooxa Sol analysis

4- [4 '- [(difluoromethyl) thio] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) -4,5-dihydrooxa Mass-produced samples of sol (purity:> 95%) were dissolved in hexane / isopropanol (80/20) at a ratio of 10-15 mg / mL. (S, S) -O 1 column (a chiral column from Regis, the Pirkle-Concept chiral stationary phase is a mixture of (S, S) -4 - (3,5-dinitrobenzamido) -tetrahydro phenanthrene), hexane / isopropanol (80/20) was used as the mobile phase to separate the obtained sample solution. All of the analytical columns (25 cm x 4.6 mm ID, Regis catalog No. 786101) and manufacturing columns (25 cm x 10 mm ID, Regis catalog No. 786102) . Approximately 10-20 mg of each enantiomer was collected within 8 hours from each column. Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- -Dihydrooxazole is the first eluting enantiomer (retention time tR on analytical column at flow rate of 1 mL / min is set to 10 min and detector wavelength set to 310 nm), (+) - 4- [4 '- [ (1,1'-biphenyl) -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydrooxazole is the second eluting enantiomer (Retention time tR on an analytical column at a flow rate of 1 mL / min is 22 min and detector wavelength is set to 310 nm).

Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- - dihydrooxazole sample has a rotation [?] ²⁰ _D of -27.8 ° +/- 0.9 ° (c 0.87, CHCl ₃ ) and a melting point of 71-73 ° C, difluoro-methyl) thio] [1,1'-biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro-oxazol-sample rotation [α] ²⁰ the _D + 27.2 ° +/- 2.0 ° (c 0.99, CHCl 3) , and a melting point of 77-78 ℃.

The following compounds of Tables 1-30 can be prepared according to the procedures described herein in conjunction with methods known in the art. The compounds of the first row of Table 1 can be referred to as 1-1, 1-2, 1-3 and 1-4 (as indicated by rows and columns). All of the other specific compounds included in these tables can be displayed in a similar manner. Abbreviations used in the table below mean Me = methyl, Et = ethyl, OMe = methoxy and OEt = ethoxy.

R ¹ = F, R ² = F, R ³ = H, R ⁵ = H, n = 0, and R ⁴ is: First column Second column Column 3 Fourth column One CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 2 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 3 CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 4 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 5 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = H, n = 1 and R ⁴ is First column Second column Column 3 Fourth column 6 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 7 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 8 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 9 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 10 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = H, n = 2 and R ⁴ is First column Second column Column 3 Fourth column 11 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 12 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 13 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 14 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 15 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = Me, n = 0, R ⁴ is: First column Second column Column 3 Fourth column 16 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 17 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 18 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 19 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 20 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = Me, n = 1 and R ⁴ is: First column Second column Column 3 Fourth column 21 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 22 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 23 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 24 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 25 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = Me, n = 2 and R ⁴ is: First column Second column Column 3 Fourth column 26 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 27 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 28 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 29 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 30 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = Et, n = 0 and R ⁴ is: First column Second column Column 3 Fourth column 31 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 32 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 33 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 34 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 35 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = Et, n = 1 and R ⁴ is: First column Second column Column 3 Fourth column 36 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 37 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 38 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 39 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 40 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = Et, n = 2 and R ⁴ is: First column Second column Column 3 Fourth column 41 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 42 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 43 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 44 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 45 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = OMe, n = 0 and R ⁴ is: First column Second column Column 3 Fourth column 46 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 47 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 48 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 49 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 50 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = OMe, n = 1 and R ⁴ is as follows: First column Second column Column 3 Fourth column 51 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 52 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 53 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 54 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 55 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = OMe, n = 2 and R ⁴ is: First column Second column Column 3 Fourth column 56 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 57 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 58 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 59 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 60 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = OEt, n = 0 and R ⁴ is: First column Second column Column 3 Fourth column 61 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 62 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 63 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 64 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 65 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = OEt, n = 1 and R ⁴ is: First column Second column Column 3 Fourth column 66 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 67 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 68 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 69 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 70 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = OEt, n = 2 and R ⁴ is: First column Second column Column 3 Fourth column 71 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 72 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 73 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 74 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 75 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = F, n = 0 and R ⁴ is First column Second column Column 3 Fourth column 76 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 77 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 78 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 79 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 80 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = F, n = 1 and R ⁴ is as follows: First column Second column Column 3 Fourth column 81 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 82 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 83 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 84 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 85 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = F, n = 2 and R ⁴ is: First column Second column Column 3 Fourth column 86 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 87 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 88 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 89 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 90 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = Cl, n = 0 and R ⁴ is: First column Second column Column 3 Fourth column 91 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 92 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 93 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 94 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 95 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = Cl, n = 1, R ⁴ is: First column Second column Column 3 Fourth column 96 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 97 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 98 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 99 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 100 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = F, R ² = F, R ³ = H, R ⁵ = Cl, n = 2 and R ⁴ is: First column Second column Column 3 Fourth column 101 CH ₂ F CHCl ₂ CHFCF ₃ CF ₂ CFCl ₂ 102 CF ₂ H CHClCF ₃ CF ₂ CF ₂ H CFClCF ₃ 103 CF ₃ CFCl ₂ CFClCF ₂ Cl CFBrCF ₃ 104 CF ₂ Cl CHFCl CCl ₂ CF ₃ CH ₂ CF ₃ 105 CF ₂ Br CFClBr CF ₂ CF ₃ CF ₂ CH ₃

R ¹ = H, R ² = F, R ³ = H, R ⁵ = H, n = 0 and R ⁴ is First column Second column Column 3 Fourth column 106 CF ₂ H CF ₂ Cl CF ₂ CF ₂ H CHClCF ₃ 107 CF ₂ Br CF ₂ CF ₃ CFClCF ₂ Cl

R ¹ = F, R ² = Cl, R ³ = H, R ⁵ = H, n = 0 and R ⁴ is: First column Second column Column 3 Fourth column 108 CF ₂ H CF ₂ Cl CF ₂ CF ₂ H CHClCF ₃ 109 CF ₂ Br CF ₂ CF ₃ CFClCF ₂ Cl

R ¹ = Cl, R ² = Cl, R ³ = H, R ⁵ = H, n = 0, R ⁴ is: First column Second column Column 3 Fourth column 110 CF ₂ H CF ₂ Cl CF ₂ CF ₂ H CHClCF ₃ 111 CF ₃ CF ₂ Br CF ₂ CF ₃ CFClCF ₂ Cl

R ¹ = H, R ² = Cl, R ³ = H, R ⁵ = H, n = 0 and R ⁴ is First column Second column Column 3 Fourth column 112 CF ₂ H CF ₂ Cl CF ₂ CF ₂ H CHClCF ₃ 113 CF ₃ CF ₂ Br CF ₂ CF ₃ CFClCF ₂ Cl

R ¹ = F, R ² = F, R ³ = H, R ⁵ = H, n = 0, and R ⁴ is: First column Second column Column 3 Fourth column 114 CF ₂ H CF ₂ Cl CF ₂ CF ₂ H CHClCF ₃ 115 CF ₃ CF ₂ Br CF ₂ CF ₃ CFClCF ₂ Cl

R ¹ = H, R ² = F, R ³ = F, R ⁵ = H, n = 0 and R ⁴ is First column Second column Column 3 Fourth column 116 CF ₂ H CF ₂ Cl CF ₂ CF ₂ H CHClCF ₃ 117 CF ₃ CF ₂ Br CF ₂ CF ₃ CFClCF ₂ Cl

R ¹ = F, R ² = Cl, R ³ = F, R ⁵ = H, n = 0 and R ⁴ is: First column Second column Column 3 Fourth column 118 CF ₂ H CF ₂ Cl CF ₂ CF ₂ H CHClCF ₃ 119 CF ₃ CF ₂ Br CF ₂ CF ₃ CFClCF ₂ Cl

R ¹ = Cl, R ² = Cl, R ³ = F, R ⁵ = H, n = 0, R ⁴ is: First column Second column Column 3 Fourth column 120 CF ₂ H CF ₂ Cl CF ₂ CF ₂ H CHClCF ₃ 121 CF ₃ CF ₂ Br CF ₂ CF ₃ CFClCF ₂ Cl

R ¹ = H, R ² = Cl, R ³ = F, R ⁵ = H, n = 0 and R ⁴ is: First column Second column Column 3 Fourth column 122 CF ₂ H CF ₂ Cl CF ₂ CF ₂ H CHClCF ₃ 123 CF ₃ CF ₂ Br CF ₂ CF ₃ CFClCF ₂ Cl

124 Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- - dihydrooxazole 125 Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- - S-form sulfoxide of dihydrooxazole 126 Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- - R-form sulfoxide of dihydrooxazole 127 Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- - dihydrooxazole sulfone

Product / Usability

The compounds of the present invention will generally be used in formulations or compositions with an agriculturally acceptable carrier comprising one or more of a liquid diluent, a solid diluent or a surfactant. The formulation or composition components are selected to match the physical properties of the active ingredient, the application method and environmental factors such as soil shape, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable thickeners), suspensions, emulsions (including microemulsions and / or suspoemulsions), which may optionally be thickened and gelled . Useful formulations include solids such as powders, powders, granules, pellets, tablets, films, etc. which may be further water-dispersible (wettable) or water-soluble. The active ingredient may be (micro) encapsulated and may be further formed into a suspension or solid preparation, or alternatively the entire formulation of the active ingredient may be encapsulated (or " overcoated "). The encapsulation may control or retard the release of the active ingredient. The sprayable agent may be diluted in a suitable medium and used in a spray amount of from about 1 to several hundred liters per hectare. High concentration compositions are mainly used as intermediates for other pharmaceuticals.

The formulation will typically contain an effective amount of the active ingredient, a diluent and a surfactant in the following approximate range up to a total amount of 100% by weight.

weight%

Active ingredient diluent surfactant

Water dispersibility and water solubility

Granulation, refining and powder 5-90 0-94 1-15

Suspensions, emulsions, solutions,

(Including emulsifiable concentrates) 5-50 40-95 0-15

Powder 1-25 70-99 0-5

Granules and pellets 0.01-99 5-99.99 0-15

High concentration composition 90-99 0-10 0-2

Exemplary solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd ed., Dorland Books, Caldwell, New Jersey. A typical liquid diluent is described in Marsden, Solvents Guide, 2nd ed., Interscience, New York, (1950). McCutcheon ' s Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey] and [Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, (1964), contains surfactants and recommended uses. All formulations may contain minor amounts of additives or thickeners to increase viscosity to reduce foaming, caking, decay, microbial growth, and the like.

Examples of the surfactant include polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzenesulfonates, organic silicones, N , N-dialkyltaurate, ligninsulfonate, naphthalenesulfonate formaldehyde thickeners, polycarboxylates, and polyoxyethylene / polyoxypropylene block copolymers. Examples of the solid phase diluent include clay, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium hydrogen carbonate, and sodium sulfate such as bentonite, montmorillonite, attapelite and kaolin . Examples of the liquid phase diluent include water, N, N-dimethylformamide, dimethylsulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, Sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, fatty acid ester; Ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

The solution agent containing the emulsifiable concentrating agent can be prepared by simply mixing the components. Powders and powders may generally be prepared by mixing in a hammer mill or a fluid energy mill and generally pulverizing. Suspensions are generally prepared by wet fractionation (see, for example, U.S. Pat. No. 3,060,084). Granules and pellets may be prepared by spraying the active material onto a preformed granular carrier or by flocculation techniques. Perry's Chemical Engineer's Handbook, Fourth Edition, McGraw-Hill, New York, (1963), pp. 8-57 et seq .; and Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp. 147-48, See International Application No. WO 91/13546. Pellets may be prepared as described in U.S. Patent No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Patents 4,144,050, 3,920,442 and DE 3,246,493. Tablets may be prepared as taught in U.S. Patent Nos. 5,180,587, 5,232,701, and 5,208,030. The film may be prepared as taught in British Patent No. 2,095,558 and U.S. Patent No. 3,299,566.

Additional information regarding the formulation field includes U.S. Patent 3,235,361, Column 6, Columns 16 through 7, Column 19 and Examples 10-41; US Patent No. 3,309,192, Column 5, Column 43 to Column 7, Column 62 and Example 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; US Patent No. 2,891,855, Column 3, line 66 to column 5, line 17 and Example 1-4, and Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961), pp 81-96; And Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, (1989).

In the following examples, all percentages are by weight and all formulations are prepared in the usual manner. Compound No. means the compound of Table A-B shown below.

Example A

Wettable powder

Compound 2 65.0%

Dodecyl phenol Polyethylene glycol ether 2.0%

Sodium lignin sulfonate 4.0%

Sodium Silicoaluminate 6.0%

Montmorillonite (calcined) 23.0%

Example B

Granulation

Compound 2 10.0%

Etapelite granules (low volatiles,

0.71 / 0.30 mm; U.S.S. No. 25-50 Seve) 90.0%

Example C

Extruded pellets

Compound 2 25.0%

Sodium sulfate anhydride 10.0%

Crude calcium ligninsulfonate 5.0%

Sodium alkylnaphthalenesulfonate 1.0%

Calcium / Magnesium bentonite 59.0%

Example D

Emulsifiable concentrate

Compound 2 20.0%

The oil-soluble sulfonate and

Blend of polyoxyethylene ether 10.0%

Isophorone 70.0%

The compounds of the present invention can be used in a wide range of leaf-feeding applications, including pests for growing and stored agricultural crops, forestry, greenhouse crops, corn crops, seedlings, storage and textile products, livestock, , Arthropods ("arthropods", including insects, mites and nematodes) that live in fruit-eating, stem or root feeding, seed feeding, aquatic and soil. Those skilled in the art will understand that not all compounds are equally effective for all growth stages of all pests. However, all of the compounds of the present invention are useful for the treatment of eggs, larvae and adults of Lepidoptera; Egg, leaf-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of Coleoptera neck; Hemiptera and Homoptera neck eggs, immature insects and adults; Eggs, larvae, larvae and adults of Acari; Eggs, immature larvae and adults of Thysanoptera, Orthoptera and Dermaptera; Eggs, immature and adults of Diptera; It exhibits activity against insects including nematode eggs, larvae and adults. The compounds of the present invention are also useful for the treatment of pests of Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera, It is active against insects belonging to the spider river and the parasite. In particular, the compounds are useful for the treatment of diseases such as Diabrotica undecimpunctata howardi, Mascrosteles fascifrons, Anthonomus grandis, Tetranychus urticae, Spodoptera frugiperda, Aphis fabae Such as Myzus persica, Aphis gossypii, Diuraphis noxia, Sitobion avenae, Heliothis wirescens, Lissorhoptrus oryzophilus, Rape beetle (Oulema oryzae), Sogatella furcifera, Nephotettix cincticeps, Nilaparvata lugens, Laodelphax striatellus, Chilo suppressalis, Rice leafhopper, Cnaphalocrocis medinalis, Scotinophara lurida, Oebalus pugnax, Leptocorisa chinensis, Cletus puntiger, and southern green odorant beds (Ne zara viridula). The compounds are active against mites and are active against Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, ), Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Aotetra Naicus Carpinii, Eotetranychus carpini borealis, Eotetranychus hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranacus vulgaris, (Eotetranychus banksi) and Oligonychus pratensis (Tetranychi < RTI ID = 0.0 >dae); Which contains Tenoviruses, including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus californicus, and Brevipalpus obovatus, And (Tenuipalpidae); Phyllocoptruta oleivora, Eriophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae (Phyllocoptruta oleivora), Eriophyes mangiferae (Eriophyidae), which contains Salan, Larval Larvae, and is active against mite indicating chemical sterilization activity. See International Application Publication Nos. WO 90/10623 and 92/00673 for a more detailed description of pests.

The compounds of the present invention may also be used in combination with other insecticides, fungicides, nematicides, bactericides, fungicides, growth regulators, chemical sterilizers, semiochemicals, repellents, attractants, pheromones, Can be combined with one or more of the other biologically active compounds to form a multicomponent killer pesticide that provides a broader range of agricultural protection. Examples of agriculturally acceptable agents that may be formulated with the compounds of the present invention include, but are not limited to, avermectin, acetic acid, acrinatrin, aralinicarb, aldicarb, aldoxycarb, alpha methrin, amitraz, But are not limited to, but are not limited to, but are not limited to, but are not limited to, but are not limited to, but are not limited to, methine, azidirachtin, azinphos-methyl, azocyclotin, Butoxycarbonyloxycarbonyl, carboxy, carbobenzothione, carbosulfan, carthope, quinomethineone, chloetocarb, chlorethoxyphosphorus, chlorobenzothiophene, (NI-25), (E) -N - [(6-chloro-3-pyridinyl) methyl] -N'-cyano-N-methyl-ethanimidamide Chlorpyrrhizolone, Chlormethos, Chlorobenzilate, Chlorpyrifos, Chlorpyriphos-methyl, Chlopentezin, Cyanophos, Cyclophos But are not limited to, threonine, threonine, threonine, threonine, threonine, threonine, threonine, threonine, But are not limited to, dichlorobenzene, dichlorobenzene, dichlofos, dichotorous, diethion, diphenyl benzene, dimethoate, dimethyl biphosph, dioxathione, disulfotone, ediphene, emamectin, But are not limited to, etofenprox, etofenprox, etrimpose penproproperm, phenaminophen, phenazanquin, penbuttinoxid, phenitrothion, phenobucarb, phenothiocarb, phenoxycarb, pen (CGA 157419), flucycloqualone, fluconitrile, fluphenoxalone, fluphenol, fenoxylate, fenoxylate, fenoxylate, Prox, toe-fluvvalinate, phonophos, formothion, postasejit, But are not limited to, proline, furothiocarb, HCH, heptenophores, hexapulumuron, hecitia, imidacloprid, ivenobenz, isazopos, isopenphos, isoprocarb, isoxathion, ivermectin, (CGA 184669), malathion, mecharbam, methosulffen, methaldhehyde, methacryphose, methamidophor, methidathion, methiocarb, methomyl, methocarbamate, (Methoxycarbonyl) [4- (trifluoromethoxy) phenyl] amino] carbonyl] indeno [2, 1,2-e] [1,3,4] oxadiazine-4a-carboxylate (DPX-JW062), milbemectin, monocrothophos, moscidetin, omeateate, oxamyl, oxydemethone M , Oxydipropos, parathion, parathion-methyl, permethrin, pentoate, phorate, phosphoryl, phosphat, phosphamidone, fores, pyrimicarb, Such as, for example, Mifos E, propenophos, promecarb, propafos, propargid, proparoid, prothiophos, protoate, pimetrozine, paireclocose, pilivene, pyrethmethrin, But are not limited to, thrombin, pyriproxyfen, pyruvate, trimer, pyridivene, pyrimidifene, pyriproxypen, pimetrozine, quinalphos, regetrin, rotenone, salitione, (RH 5992), Tebupenfilad, Tebufinrimos, Teflubenjuron, Teflutrin, Temepos, Terbam, Terebufos, Tetrachlorobinphos, Thiopanox, Thiodicarb, Thiopa Such as xanthone, thioxanthone, thionazine, trilomethrin, triarathene, triazophor, trichlorfon, triflumuron, trimethacarb, vimidothione, XMC, xylicarb and zeta-cypermethrin Pesticides, nematicides and biting agents; (ICIA 5504), benalazyl, benodanil, benomyl, binaparcyl, biphenyl, biterthanol, blasticidin-S < RTI ID = 0.0 > , Bordeaux mixture (tribasic copper sulfate), bromuconazole, bupirimate, butthiobate, caftaphole, caftan, carbendazim, carboxym, cynomethonate, chlorynev, chloropycin, Cyprodinil (CGA 219417), cyprodinil (CGA 219417), cyprofuran, cyprodinil, cyprodinil, cyprodinil, cyprodinil, But are not limited to, dichlorophenol, dichlorophenol, dichlorobenzene, dichlorobenzene, dichlorophen, dichlorobutazole, dichlorofuranide, dichloromethane, dichlororan, dicopol, dienochlor, diethophenecarb, difenoconazole, dimethyimol, dimethomorph, , Diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalaphosphate, dithianzone, Phenanthroline, phenothiophene, phenanthroline, phenothiophene, phenothiophene, phenothiophene, phenothiophene, phenothiophene, phenothiophene, But are not limited to, propylmorph, pentyneacetate, pentynehydroxide, perbam, perimin, fluazinam, furdioxo, fulloomide, fluquinone, fluosilazole, But are not limited to, polyols, polyphenols, polypethols, fosetyl-aluminum, fueridazole, furalacyl, furerecylox, guazatine, hexachlorobendazole, hexaconazole, (BAS 490 F), mancofer, mancozeb, maneb, mephanipyrim, mepronil, me- lalatol, mefenacin, (E) -2- (methoxyimino) -N-methyl-2- (2-phenoxyphenyl) acetic acid, methosulfuric acid But are not limited to, thiamidometallam (SSF-126), methsulfobox, Michaelobutanyl, neo-asophilization (ferric methane arsenate), nitrotalisopropyl, norarimol, But are not limited to, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene Pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, pyruvate, But are not limited to, benzothiazole, benzothiazole, thiadiophene, thiophenate-methyl, thiam, tolclofos-methyl, tolylfluanide, triadimefon, triadimenol, triazole, triclumide, Tricyclophosphate, tricyclodecanone, tricyclodecanone, tricyclodecanone, tricyclodecanone, Live like Neve and jiram fungicide; Streptomycin and bactericides; And biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus and insect pathogenic bacteria, viruses and fungi.

In certain cases, incorporation with other animal prophylaxis agents having similar efficacy ranges but differing action types may be particularly advantageous for tolerance management.

In order to better control the pests (rate of use or range), or to control tolerance, it is possible to use pesticides such as abamectin, penproperin, fipronil, imidacloprid, methomayil, propargite, pyridaben, tebufenozide, Pyrethroids, and mixtures of the compounds of the present invention. Particularly preferred mixtures are compounds 2 and abamectin; Compound 2 and penproperrin; Compound 2 and fipronil; Compound 2 and imidacloprid; Compound 2 and methomyl; Compound 2 and propargite; Compound 2 and pyridabene; Compound 2 and tebufenozide; Compound 2 and Tebufenpylar; Compound 3 and abamectin; Compound 3 and penproperrin; Compound 3 and fipronil; Compound 3 and imidacloprid; Compound 3 and methomayil; Compound 3 and propargite; Compound 3 and pyridabene; Compound 3 and tebufenozide; Compound 3 and Tebufenpylar; Compound 4 and abamectin; Compound 4 and penproperrin; Compound 4 and fipronil; Compound 4 and imidacloprid; Compound 4 and methomale; Compound 4 and propargite; Compound 4 and pyridabene; Compound 4 and tebufenozide; Compound 4 and tebufenpyrad (Compound No. means compound of Index Table A-B).

Arthropod pests may be used to control and protect agricultural crops, horticultural crops, and specialty crops, and animal and human hygiene may include one or more effective amounts of a compound of the invention in an environment of pests, including infested cropland and / , Or directly to the pest to be controlled. That is, the present invention also relates to the use of a composition comprising one or more compounds of the present invention and one or more compounds of the present invention in an effective amount of a pest environment, including the infested farmland and / or non-farmland, , Methods of controlling arthropods and nematodes inhabiting leaves and soils, and methods of protecting agricultural and / or non-agricultural crops. A preferred application method is spraying. Alternatively, the granular formulations of the present compounds may be applied to plant leaves or soils. Other application methods include direct application methods and methods such as residual spraying, aerosol spraying, seed coating, microencapsulation, systemic absorption, bait, eartag, bolus, fogger, , Aerosol method, blowing method and many other methods. The compound may be incorporated into a device such as a trap or the like that is consumed by arthropods.

The compounds of the present invention may be applied in a pure state, but most application forms will be preparations which, together with one or more compounds, contain suitable carriers, diluents and surfactants and possibly food according to the intended end use. A preferred method of application comprises spraying an aqueous dispersion or an emulsion of the compound. Often, the efficacy of the compound is enhanced in combination with a synergistic agent such as spray oil, spray oil concentrate, spray sticker, adjuvant, other solvent, and butoxy piperoneil.

The rate of application required for effective control depends on factors such as the species of arthropod to be controlled, the life cycle of the insect, life stage, pest size, location, age, host crop or animal, feeding type, mating type, atmospheric humidity, will be. In normal circumstances, an application rate of about 0.01 to 2 kg of active ingredient per hectare is effective in controlling insects in agricultural ecosystems, but about 0.001 kg per hectare may be sufficient, or as much as 8 kg. For non-agrochemical applications, the effective utilization rate is about 1.0 to 50 mg per square meter, but about 0.1 mg per square meter may be sufficient, or about 150 mg may be needed.

The next test is to demonstrate the control efficacy of the compounds of the invention against certain pests. &Quot; Control efficacy " refers to inhibition of arthropod growth (including mortality), which significantly reduces feeding. However, the pest control protection provided by the compounds is not limited to these species. Refer to Index Table A-B for compound specifications. Abbreviations used in the index table are Me = methyl, Et = ethyl, OMe = methoxy and OEt = ethoxy.

<Index Table A>

* Refer to Index Table B for ¹ H NMR data.

<Index table B>

^a &lt; ¹ &gt; H NMR data are located in the ppm down field from tetramethylsilane. Coupling is expressed as (s) for a single line, (t) for a triple line, (q) for a quadruple line, and (m) for a multiple line.

The biological example of the present invention

Test A

Larval 2 point spider mite (Tetranychus urticae)

The test compound solution was dissolved in a minimal amount of acetone, and the wetting agent-containing water was then added until the concentration of the compound was 50 ppm. Two-point spider mite The infected two-week-old red kidney bean plants were sprayed with the test solution (equivalent to 28 g per hectare) soaked with a rotary atomizer. The plants were placed in a chamber at 25 ° C and 50% relative humidity. Of the compounds tested, 1, 2, 3, 4, 5, 6, 7, 8, 9 ^* , 10 ^* , 11 ^* , 12 ^** , 13 ^* , 14 ^* , 15 ^* , 16 ^** , 17 ^** , 18 ^** , 19 ^* and 23 ^** showed more than 80% killer / salancer activity after more than 7 days of spraying.

^The compounds were sprayed at a concentration of 5 ppm (corresponding to 2.8 g / ha).

^** Compound was sprayed at a concentration of 0.5 ppm (corresponding to 0.28 g / ha).

Test B

Whole plant test

The test compound solution was dissolved in a minimal amount of acetone, and the wetting agent-containing water was then added until the concentration of the compound was 10 ppm. Then, the soybean plants were sprayed with the test compound (corresponding to 5.5 g / ha) so as to soak using a rotary platform and atomizing atomizer. The test plants were dried and excised to expose the Spodoptera frugiperda larva to the treated leaves. The test units were placed at 27 ° C and 50% relative humidity, infected and the larval mortality measured after 120 hours. Among the compounds tested, 2 ^*, 3 ^*, 4 ^*, 5, 6, 7, 8, 9, 10, 11, 12 ^**, 13, 14, 15 ^**, 16 ^*, 17 ^*, 18 ^*, 19 And 23 ^** showed more than 80% mortality.

^The compounds were sprayed at a concentration of 3 ppm (corresponding to 1.6 g / ha).

^** Compound was sprayed at a concentration of 0.3 ppm (corresponding to 0.16 g / ha).

Claims (17)

Compounds of formula &lt; RTI ID = 0.0 &gt; (I) &lt; / RTI & (I) Wherein, R &lt; ¹ &gt; is H, F or Cl; R ² is F or Cl; R &lt; ³ &gt; is H or F; R ⁴ is C ₁ -C ₂ haloalkyl; R ⁵ is H, F, Cl, C ₁ -C ₂ alkyl, or C ₁ -C ₂ alkoxy; n is 0, 1 or 2; With the proviso that when i) R ² is F, R ³ and R ⁵ are H and n is 0, R ⁴ is other than CF ₃ ; ii) when R ¹ is F, R ² is Cl, R ³ and R ⁵ are H, and n is 0, then R ⁴ is other than CF ₃ . The method according to claim 1, R ¹ and R ² are F; R ³ is H; R ⁴ is CF ₂ H, CF ₃ , CF ₂ Br, CF ₂ CF ₂ H or CF ₂ CF ₃ . The method according to claim 1, R ¹ , R ² and R ³ are F; R ⁴ is CF ₂ H, CF ₃ , CF ₂ Br, CF ₂ CF ₂ H or CF ₂ CF ₃ . The method according to claim 1, R &lt; ¹ &gt; is F; R ² is Cl; R &lt; ⁵ &gt; is H 5. The method of claim 4, 2- (2-Chlorophenyl) -4- [4 '- [(difluoromethyl) thio] [1,1'-biphenyl] -4-yl] -4,5-dihydrooxazole; 2- (2-Chlorophenyl) -4- [4 '- [(difluoromethyl) sulfinyl] [1,1'-biphenyl] -4-yl] -4,5-dihydrooxazole; And The group of 2- (2-chlorophenyl) -4- [4 '- [(difluoromethyl) sulfonyl] [1,1'- biphenyl] -4-yl] -4,5-dihydrooxazole &Lt; / RTI &gt; 3. The compound according to claim 2, wherein R &lt; ⁵ &gt; The compound according to claim 6, wherein R ⁴ is CF ₂ H, CF ₃ or CF ₂ Br. 8. The method of claim 7, 4- [4 '- [(difluoromethyl) thio] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) -4,5-dihydrooxa Sol; 4- [4 '- [(difluoromethyl) sulfinyl] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) -4,5- Oxazole; 4- [4 '- [(difluoromethyl) sulfonyl] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) -4,5- Oxazole. &Lt; / RTI &gt; 9. The method of claim 8, 4- [4 '- [(difluoromethyl) thio] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) -4,5-dihydrooxa Lt; / RTI &gt; 9. The method of claim 8, 4- [4 '- [(difluoromethyl) sulfinyl] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) -4,5- Oxazoline. 9. The method of claim 8, 4- [4 '- [(difluoromethyl) sulfonyl] [1,1'-biphenyl] -4-yl] -2- (2,6- difluorophenyl) -4,5- Oxazoline. 10. The method of claim 9, Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- - dihydrooxazole. 11. The method of claim 10, Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- - &lt; / RTI &gt; S-sulfoxide of dihydrooxazole. 11. The method of claim 10, Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- Lt; RTI ID = 0.0 &gt; R-form &lt; / RTI &gt; sulfoxide of dihydrooxazole. 12. The method of claim 11, Biphenyl] -4-yl] -2- (2,6-difluorophenyl) -4,5-dihydro- - &lt; / RTI &gt; dihydrooxazole. Wherein the composition comprises at least one compound of claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent. A method of controlling arthropod comprising contacting an arthropod or an arthropod-effective amount of a compound of claim 1 in its environment.