TITLE ARTHROPODICIDAL BENZAMIDES BACKGROUND OF THE INVENTION

This invention relates to certain benzamides, their agriculturally suitable salts and compositions, and methods of their use as arthropodicides in both agronomic and nonagronomic environments.

The control of arthropod pests is extremely important in achieving high crop efficiency. Arthropod damage to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of arthropod pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.

JP 7[1995]-188137 discloses benzamides of Formula i as insecticides:

wherein

X is, inter alia, optionally substituted phenyl; n is an integer from 1-5;

Y is, inter alia, halogen; m is an integer from 1-5;

Z is , inter alia, halogen or optionally substituted alkylsulfonyloxy; and

A is optionally substituted methylene.

The benzamides of the present invention are not disclosed in this publication. SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula I including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use as arthropodicides:

wherein

X is H, F or Cl; Y is F or Cl; Z is H or F;

R ¹ is Br, I or OR ³ ;

R ² is phenyl substituted in ϋie para position with R ⁴ ; or phenylethynyl substituted on the phenyl ring in the para position with R ⁵ ; R ³ is C _r C ₃ alkylsulfonyl; R ⁴ is C , -C ₃ haloalkoxy, C _j -C ₃ haloalkylthio, C , -C ₃ haloalkylsulfmyl, C , -C ₃ haloalkylsulfonyl or trifluoromethylsulfonyloxy; and R ⁵ is halogen, cyano, C1-C ₄ alkyl, C _r C ₃ haloalkyl, C1-C3 alkoxy, C _r C ₃ haloalkoxy, Cι-C ₃ haloalkylthio, Cj-C ₃ haloalkylsulfmyl, C _r C ₃ haloalkylsulfonyl or trifluoromethylsulfonyloxy. In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, rc-propyl, /-propyl, or the different butyl isomers. "Alkoxy" includes, for example, methoxy, ethoxy, w-propyloxy, or isopropyloxy. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio isomers. "Alkylsulfmyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfmyl" include CH ₃ S(O), CH ₃ CH ₂ S(O), CH ₃ CH ₂ CH ₂ S(O), and (CH ₃ ) ₂ CHS(O). Examples of "alkylsulfonyl" include CH ₃ S(O) ₂ , CH ₃ CH ₂ S(O) ₂ , CH ₃ CH ₂ CH ₂ S(O) ₂ , and (CH ₃ ) ₂ CHS(O) ₂ .

The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F ₃ C, C1CH ₂ , CF ₃ CH ₂ and CF ₃ CC1 ₂ . The terms "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF ₃ O, CCl ₃ CH ₂ O, HCF ₂ CH ₂ CH ₂ O and CF ₃ CH ₂ O. Examples of "haloalkylthio" include CC1 ₃ S, CF ₃ S, CC1 ₃ CH ₂ S and C1CH ₂ CH ₂ CH ₂ S. Examples of "haloalkylsulfmyl"

include CF ₃ S(O), CCl ₃ S(O), CF ₃ CH ₂ S(O) and CF ₃ CF ₂ S(O). Examples of "haloalkylsulfonyl" include CF ₃ S(O) ₂ , CCl ₃ S(O) ₂ , CF ₃ CH ₂ S(O) ₂ and CF ₃ CF ₂ S(O) ₂ .

The total number of carbon atoms in a substituent group is indicated by the "C _j -C _j " prefix where i and j are numbers from 1 to 4. For example, Cι-C ₃ alkylsulfonyl designates methylsulfonyl through propylsulfonyl.

When a group contains a substituent which can be hydrogen, for example X or Z, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.

Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.

The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group. Preferred compounds for reasons of better activity and/or ease of synthesis are:

Preferred 1. Compounds of Formula I above, and agriculturally suitable salts thereof, wherein: Z is H;

R ¹ is I or OR ³ ; R ² is phenyl substituted in the para position with R ⁴ ; and

R ³ is methylsulfonyl. Preferred 2. Compounds of Preferred 1 wherein:

R ⁴ is difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio, difluoromethylsulfinyl, trifluoromethylsulfinyl, difluoromethylsulfonyl, trifluoromethylsulfonyl or trifluoromethylsulfonyloxy.

Preferred 3. Compounds of Formula I above, and agriculturally suitable salts thereof, wherein: Z is H;

R ¹ is I or OR ³ ; R ² is phenylethynyl substituted on the phenyl ring in ihe para position with R ⁵ ; and R ³ is methylsulfonyl. Preferred 4. Compounds of Preferred 3 wherein:

R ⁵ is difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifiuoromethylthio, difluoromethylsulfinyl, trifluoromethylsulfinyl, difluoromethylsulfonyl, trifiuoromethylsulfonyl or trifluoromethylsulfonyloxy. Most preferred are compounds of Formula I selected from the group: N-[2-bromo-l-[4 ^* -[(difluoromethyl)thio][l,l ^, -biphenyl]-4-yl]ethyl]-2,6- difluorobenzamide;

N-[l -[4'-[(difluoromethyl)thio][l ,1 '-biρhenyl]-4-yl]-2- [(methylsulfonyl)oxy]ethyl]-2,6-difluorobenzamide; and N-[l -[4'-[(difluoromethyl)thio][l ,1 '-biphenyl]-4-yl]-2-iodoethyl]-2,6- difluorobenzamide. This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds.

This invention also relates to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of the compounds of the invention (e.g., as a composition described herein). The preferred methods of use are those involving the above preferred compounds.

DETAILS OF THE INVENTION The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-11. The definitions of all variables in the compounds of Formulae I-XII below are as defined above in the Summary of the Invention.

The compounds of Formula I used as effective ingredients in this invention can, for example, be prepared by the chemistry shown in Scheme 1 with compounds of Formula II. Such chemistry of the opening of 2-aryloxazolines can be found in Frump, Chemical Reviews, 71, 494-496 (1971) and Goldberg and Kelly, J. Chem Soc, 1919 (1948).

Scheme 1

The ring opening reaction of compounds of Formula II, an oxazoline, can be carried out at 0-60 °C by treatment of a solution of a compound of Formula II in diethyl ether with a strong acid HR ¹ (R ¹ = Br, I, OSO ₂ CH ₃ ) in aqueous solution over a few hours to a few days. The two phase reaction mixture can be readily separated by extraction and the compound of Formula I is present in the ether layer. However, this chemistry of Scheme 1 also produces various amount of the ammonium salts III which are present in the aqueous layer (Scheme 2). Compounds of Formula III may be very soluble in aqueous solution or may be very insoluble in aqueous solution depending on the hydrophilicity and hydrophobicity of the rest of the molecule.

Scheme 2

Water III

If the compounds of Formula III are insoluble in the aqueous solution, they can be readily filtered and cleaned up by washing with ether to remove organic impurities.

Compound III can be used in making compounds of Formula IV (Scheme 3). If the compounds of Formula IV are soluble in the aqueous solution, they can be isolated by evaporating the aqueous solution containing the compound of Formula III to dryness followed by treatment with diethyl ether to crystallize the compound of Formula III.

When compounds of Formula II are treated with HR ¹ in methanol at room temperature, the respective of compound of Formula III can be isolated in almost quantitative yield. Unlike ether, methanol does not produce much compound of Formula I under this condition. A recent reference can be found in Murakami et al., Tetrahedron Lett., 35, 745 (1994).

Compounds of Formula IV can be readily prepared by treatment of a slurry of a compound of Formula III in a polar solvent such as acetonitrile with a suitable base such as DBU (l,8-diazabicyclo[5.4.0]undec-7-ene) at room temperature. The reaction is essentially complete upon mixing. Workup of the reaction is typically carried out by evaporating the acetonitrile under vacuum, and extracting the residue with methylene chloride and 1 N HCl solution. Compounds of Formula IV can be obtained in almost quantitative yield.

Scheme 3

IV

In addition to the chemistry shown in Scheme 3, compounds of Formula IV are generally synthesized from substituted benzoyl chlorides and substituted phenylglycinols. Many of these synthetic methods of compounds of Formula IV are described in WO 95/04726.

Compounds of Formula IV can be readily converted to compounds of Formula I (Scheme 4) following various procedures in the chemical literature. These procedures typically employ selective reagents for certain compounds of Formula I such as PBr ₃ in Organic Synthesis IV, 106, (1963), PPh ₃ /Br ₂ in Smalec and Vonitzstein, Carbohydrate Research 266, 269 (1995), PPh ₃ /I ₂ in Nakata, Tetrahedron Lett., 32, 5363 (1991) and in Rozwadowska, Tetrahedron-Asymmetry, 4, 1619 (1993).

Scheme 4

PPh ₃ /Br2 or

IV

PPh ₃ /i2 _{(Rl = Brι I)}

Upon treatment with an alkylsulfonyl chloride and an organic base, compounds of Formula IV are readily converted to compounds of Formula I (R ¹ = OR ³ ) (Scheme 5).

Scheme 5

IV + R ³ Cl + base

(Rl = OR ³ )

Additional methods of synthesis of compounds of Formula I are shown in Schemes 6-8. Following the literature references by Drefahl and Ponsold, Chem. Ber , PJ, 519 (1960) and Hassner and Heathcock, J. Org Chem., 32, 549 (1967), compounds of Formula V can be readily synthesized from styrenes and in situ formed iodine isocyanates (INCO) in ether.

Compounds of Formula V will react with lithiated arenes such as compounds of Formula VI to form compounds of Formula I.

Scheme 6

(Rl = Br, I)

When compounds of Formula VII are deprotonated to the dianion and then treated with gaseous formaldehyde, compounds of Formula IV can be obtained in good yield as

described in Tischler and Tischler, Tetrahedron Lett., 3 (1978) and in Sell, Aust. J. Chem., 28, 1383 (1975). Compounds of Formula IV are readily converted to compounds of Formula 1 per Schemes 4 and 5.

Scheme 7

VII

Compounds of Formula I can be obtained by the decarboxylation of compounds of Formula VIII as shown in Scheme 8. These reactions include the Hunsdiecker reaction (HgO/B^/CCVlight or heat), the free radical reaction of the carboxylic esters of 2-mercaptopyridine-N-oxide developed by Barton, Tetrahedron 41, 4347-4357 (1985), and the photodecarboxylation of the benzophenone oxime esters in Hasebe and Tsuchiya, Tetrahedron Lett., 29, 6287 (1988).

VIII I

The compounds of Formula II where R ² = phenylethynyl substituted on the phenyl ring in the para position with R ⁵ are readily available by the methods described in WO 95/04726. The compounds of Formula II where R ² = phenyl substituted in the para position with R ⁴ can be prepared by the steps shown in the following reaction schemes with the compound of Formula IX. The compound of Formula IX, 2-(2,6-difluorophenyl)-4,5-dihydro-4-(4-iodophenyl)oxazole, can be prepared by the methods described in WO 95/04726. The reaction of Scheme 9 is carried out at -78 °C to the boiling point of an inert solvent selected from tetrahydrofuran, ethyl ether, hexane, toluene, etc., for 30 min to ⁿ 2 h with a transition metal catalyst, for example, bis( 1 ^-diphenylphosphinoethanej.uckeKII) chloride, tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, or palladium(II) acetate with, for example, tri-ortΛo-tolylphosphine or

triphenylarsine, and with or without the presence of added cofactors, for example, lithium chloride, copper(I) iodide, or dialkyl- or trialkylamines, to give compounds of

Formula X.

Scheme 9

R6 = I, Br, OSθ2CF ₃₎ OS0 ₂ F, etc.

R ⁷ = C\-C2 haloalkyl or a protecting group

Met = MgX, ZnX (X = Cl, Br, I),

SnMe3, SnBu ₃ , B(OH) ₂ , etc.

Intermediates of Formula IX are prepared by procedures known in the art. R ⁷ can be, as needed for ease of synthesis, a sulfur-protecting group such as t-butyldimethylsilyl, triisopropylsilyl, t-butyl, /j-methoxybenzyl, etc.

If R ⁷ is a protecting group, compounds of Formula II are prepared by deprotection of the sulfur and further reaction, as in Scheme 10. The reactions of intermediates of Formula XI are carried out in an optional, inert solvent selected from tetrahydrofuran, dioxane, ethyl ether, dichloromethane, hexane, toluene, etc., for 5 min to 72 h at -20 °C to the boiling point of the solvent. Reaction with a hydrohalocarbon, such as chlorodifluoromethane, chloroform, etc., and a base, such as sodium hydroxide, potassium hydroxide, potassium t-butoxide, etc., optionally in the presence of a phase-transfer catalyst, or alternatively, with a hydrohalo- or halocarbon substituted with a leaving group, such leaving group being iodide, bromide, chloride, methanesulfonate,/?-toluenesulfonate, etc., optionally in the presence of a base, for example, sodium hydride, sodium hydroxide, potassium hydroxide, potassium t-butoxide, etc., and optionally in the presence of a phase-transfer catalyst gives

compounds of Formula II. A compound of Formula XI can alternatively react with an activated alkene, such as tetrafluoroethylene, in the presence of an optional basic, acidic, or radical catalyst. Alternatively, the mercaptan of Formula XI can be oxidized to a disulfide (see p 1092 of Advanced Organic Chemistry, 3rd edition, J. March, (1985), John Wiley and Sons, New York) and converted to a compound of Formula I by reaction with perhaloalkanes and a radical initiator (see, for example, C. Wakselman, et al, J. Chem. Soc, Chem. Commun., (1991), 993).

Mild

CHR ⁹ ₃ R8-L CF ₂ = CF ₂ oxidation: Base (PTC) (Base) (catalyst) R8-L

(PTC) f catalyst

II II II II

R ⁸ = Cι-C ₂ haloalkyl

R9 = F, Cl, Br, I (can be mixed)

L = Cl, Br, I

PTC = phase-transfer catalyst, such as BnEt ₃ N ⁺ or n-Bu4N ⁺ salts.

Compounds of Formula II are also prepared as in Scheme 11. A compound of Formula IX is converted to a stannyl derivative of Formula XII by its reaction with, for example, hexamethyldistannane under catalysis by a metal complex, such as tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, or palladium(II) acetate with, for example, tri-ortλo-tolylphosphine, triphenylarsine, etc., with or without the presence of added cofactors, for example, lithium chloride, copper(I) iodide, dialkyl- or trialkylamines, etc. The stannyl derivative of Formula XII is then reacted with a substituted aromatic derivative of Formula XIII in the presence of a catalytic metal complex such as those noted above to afford a compound of Formula X which again is a compound of Formula II or, if R ⁶ is a protecting group, can then be converted by the chemistry of Scheme 10 to a compound of Formula II.

Scheme 11

IX XII

R ⁷ = C j -C ₃ haloalkyl or a protecting group n = 0, 1, 2

The compounds of Formula II in which R ⁴ or R ⁵ are Cj-C ₃ haloalkylsulfmyl or C1 -C3 haloalkylsulfonyl can be prepared from the compounds of Formula II where R ⁴ or R ⁵ are CpC ₃ haloalkylthio by the action of mild oxidants, for example, organic peracids, sodium periodate, etc. (see, for example, March, cited previously, pp 1089-1090, etc.). Alternatively, intermediates such as those of Formula XIII, for example, in which n = 1 or 2, give products of Formula II with R ⁴ as C _j -C ₃ haloalkylsulfmyl or C _r C ₃ haloalkylsulfonyl by the chemistry of Scheme 11. The desired product can be prepared by carrying out conventional post-reaction procedures, such as extraction, filtration, and concentration, and if needed further purified appropriately by such means as chromatography and/or crystallizations.

It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incoφoration of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I.

One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic,

radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. ¹ H NMR spectra are reported in ppm downfield from tetramethylsilane; m = multiplet. EXAMPLE 1

Step A: Preparation of [(4-bromophenvDthioltrisπ-methylethvDsilane

To a solution of 45 grams of 4-bromothiophenol in 250 mL of THF was added 53 mL of triisopropylsilyl chloride and 38 mL of DBU (l,8-diazabicyclo[5.4.0]undec-7- ene) under a nitrogen atmosphere. The reaction mixture heated spontaneously to reflux. The reaction mixture was allowed to cool and was diluted with 500 mL of hexanes. The resultant white suspension was filtered through a pad of Celite®, and the filter cake was washed with additional hexanes and 100 mL of ether. The filtrate was washed with ice-cold 0.1 N aqueous HCl, water, aqueous NaHCO ₃ , and saturated aqueous NaCl, dried over MgSO4, and concentrated under vacuum to obtain 82 grams of the title compound of Step A as a clear oil. ^! H NMR (CDC1 ₃ , 300 MHz) δ 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 - methylethvDsilyllthio]|T.r-biphenyll-4-yl1oxazole 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 below -65 °C and then 4.7 mL of 2.5 M n-BuLi/hexanes 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 was added to a solution of 201 mg of tri(o-tolyl)phosphine in 5 mL of THF, and this mixture was stirred for 5 minutes before its addition, via cannula, to the main reaction mixture. A solution of 3.85 g of 2-(2,6-difluorophenyl)-4,5-dihydro-4-(4- iodophenyl)oxazole (prepared as described in WO 95/04726) in 10 mL of THF was added, and the reaction mixture was allowed to warm to room temperature and stir for 2 to 3 hours. The reaction mixture was poured into ice-cold aqueous NH4CI and extracted with ethyl acetate. The organic phase was washed with saturated aqueous NaCl, dried over MgSO ₄ , and concentrated under vacuum. The oily residue was adsorbed onto silica gel , applied to a column of silica gel and eluted with hexane/ethyl acetate (6: 1 v:v) to obtain 3.6 g of the title compound of Step B as a viscous oil. 'H NMR (CDC1 ₃ ,

300 MHz) δ 1.1 (m,18H), 1.3 (m,3H), 4.3 (m,lH), 4.8 (m,lH), 5.5 (m,lH), 7.0 (m,2H), 7.3-7.5 (m,5H), 7.5-7.6 (m,4H).

Step C: Preparation of 4-[4'-[(difluoromethvnthioiπ.l'-biphenyll-4-yll-2-(2.6- difluorophenyl)-4.5-dihvdrooxazole To a solution of 10.9 g of the title compound of Step B in 20 mL of THF was added 23 mL of a commercial 1.0 M solution of /J-BU ₄ NF in THF (containing 5% water) at 15 to 20 °C (water bath cooling) under a nitrogen atmosphere. After 5 minutes, 5.9 g of freshly-ground KOH was added, and then excess Freon 22 (chlorodifluoromethane) was added through a subsurface tube at a rate sufficient to maintain a slight overpressure. After 20 to 30 minutes, the gas addition was stopped, and the reaction mixture was poured into ice-cold aqueous NFI ₄ CI and extracted with ethyl acetate. The organic phase was washed with water and saturated aqueous NaCl, dried over MgSO4, and concentrated under vacuum. The residue was adsorbed onto silica gel, applied to a column of silica gel and eluted with hexanes/ethyl acetate (4:1 to 3:1 v:v) to obtain an oil. The oil crystallized upon trituration with ether and hexane to produce a white solid that was dried to provide 6.2 g of the title compound of Step C as a solid melting at 72-76 °C. Η NMR (CDC1 ₃ , 300 MHz) δ 4.3-4.4 (m,lH), 4.8 (m,lH), 5.5 (m,lH), 6.85 (m,lH), 7.0 (m, 2H), 7.4-7.7 (m,9H). Step D: Preparation of N-r2-bromo-l-[4'-f(difluoromethyl)thio]π ,1 '-biphenyll-4- yl]ethyll-2.6-difluorobenzamide

To a solution of 50 mg of the title compound of Step C in 5 mL of diethyl ether at 0 °C was added 10 mL of 48% HBr solution and the resulting reaction mixture was stirred at room temperature for 18 h. The reaction mixture was poured onto ice water and extracted with diethyl ether (2 x 50 mL). The ether extracts were combined and back washed with water (100 mL). The ether layer was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The crude product was dissolved in 5 mL of n-butyl chloride and then treated with 30 mL of rc-hexane and filtered to give 15 mg of the title compound of Step D, a compound of the invention, as a solid melting at 129-130 °C. 'H ΝMR (CDC1 ₃ , 300 MHz) δ 3.80-4.00 (m,2H), 5.60-5.64 (m,lH), 6.62 (m,lH), 6.85 (m,lH), 7.00 (m,2H), 7.40-7.70 (m,9H).

EXAMPLE 2

Preparation of N-π-r4'-r ⁽ difluoromethvnthio1fl.l'-bi ^p henvn-4-yll-2-iodoethvn-2.6- difluorobenzamide To a solution of 300 mg of the title compound of Step C in Example 1 in 10 mL of diethyl ether at 0 °C was added 10 mL of 57% HI solution and the resulting reaction mixture was stirred at room temperature for 18 h. The reaction mixture was poured onto ice water and extracted with diethyl ether (2 x 50 mL). The ether extracts were combined and back washed with water (100 mL). The ether layer was dried over

magnesium sulfate, filtered and evaporated under reduced pressure. The crude product was dissolved in 5 mL of n-butyl chloride and then treated with 30 mL of n-hexane and filtered to give 280 mg of the title compound of Example 2, a compound of the invention, as a solid melting at 132-137 °C. »H NMR (CDC1 ₃ , 300 MHz) δ 3.65 (m,2H), 5.40 (m,lH), 6.64 (d,lH), 6.93 (m,3H), 7.45 (m,3H), 7.62 (m,5H).

EXAMPLE 3 Preparation of N-[2-bromo-l-r4-| ^' (4-fluorophenyl)ethynyl]phenynethyl]-2.6- difluorobenzamide To a solution of 1 g of 2-(2,6-difluorophenyl)-4-[4-[(4- fiuorophenyl)ethynyl]phenyl]-4,5-dihydrooxazole (prepared as described in

WO 95/04726) in 50 mL of ethyl ether was added 50 mL of 48% HBr. The mixing was exothermic. The reaction mixture was stirred at room temperature for 18 h and then extracted with ether (2 x 50 mL) and water. The ether extracts were combined, backwashed with water (100 mL), dried over magnesium sulfate, filtered and evaporated under vacuum to yield a crude product. Upon trituration with n-butyl chloride, the slurry was filtered and dried to give 0.80 g of the title compound of Example 3, a compound of the invention, as a solid melting at 163-164 °C. *H ΝMR (CDC1 ₃ , 300 MHz) δ 3.80-3.84 (m,2H), 5.60 (m,lH), 6.60 (m,lH), 7.00 (m,4H), 7.40 (m,3H), 7.52 (m,4H). EXAMPLE 4

Step A: Preparation of 2-amino-2-[4-r(4-fluoroρhenyl)ethynvπphenyl1ethyl 2.6- difluorobenzoate hvdrochloride To a solution of 6 g of 2-(2,6-difluorophenyl)-4-[4-[(4- fluorophenyl)ethynyl]phenyl]-4,5-dihydrooxazole in 150 mL of methanol chilled to 10 °C was added 40 mL of 1 Ν HCl dropwise. The resulting reaction mixture was stirred at 25 °C for 18 h and the cloudy solution was filtered through Celite®. The filtrate was evaporated under vacuum to yield a solid paste which was added to ether (100 mL) and filtered. The filter cake was washed with water and ether twice. After drying in air, 6.5 g of the title compound of Step A was obtained. 'H ΝMR (Me ₂ SO-fifg, 300 MHz) δ 4.65-4.82 (m,3H), 7.28 (m,4H), 7.62 (m,7H), 8.92 (s,3H).

Step B: Preparation of 2.6-difluoro-N-f 1 -[4-[(4-fluorophenyl)ethvnyl]phenyl1-2- hvdrox vethyl lbenzamide The title compound of Step A (6.5 g) was slurried in 150 mL of acetonitrile and then treated with 5 g of DBU (l,8-diazabicyclo[5.4.0]undec-7-ene) to form a clear solution. TLC showed reaction complete after 30 min. The reaction mixture was stirred for 18 h at 25 °C. The reaction mixture was evaporated under vacuum to dryness and then extracted with ethyl acetate and water. The ethyl acetate extracts were combined, dried over magnesium sulfate, filtered and evaporated to crude product. After

triturating with n-butyl chloride, the solid was filtered and air dried to afford 6.8 g of the title compound of Step B. >H NMR (Me ₂ SO-</ ₆ , 300 MHz) δ 3.62 (m,2H), 4.94-5.10

(m,2H), 7.10-7.70 (m,l IH), 9.20 (d,lH).

Step C: Preparation of 2,6-difluoro-N-π-f4-r(4-fluorophenyl)ethvnyl]phenyl]-2- [(methylsulfonvOoxylethyllbenzamide

To a solution of 0.36 g of the title compound of Step B in 20 mL of dry tetrahydrofuran was added 0.12 g of methanesulfonyl chloride and then 0.12 g of triethylamine was added dropwise. The cloudy solution was stirred at 23 °C for 18 h.

The reaction mixture was extracted with diethyl ether and water. The ether extracts were combined and evaporated under vacuum to give a white solid which was triturated with n-butyl chloride and filtered. After drying, 150 mg of the title compound of

Step C, a compound of the invention, was obtained as a solid melting at 135-137 °C.

^J H ΝMR (Me ₂ SO-d ₆ , 300 MHz) δ 3.18 (s,3H), 4.40 (m,2H), 5.44 (m,lH), 7.20-7.36

(m,4H), 7.50-7.70 (m,7H), 9.58 (d,lH). By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 2 can be prepared. The following abbreviations are used in the Tables which follow: Me = methyl, Et = ethyl, OMe = methoxy,

OEt = ethoxy, CΝ = cyano, and S(O) ₂ Me = methylsulfonyl.

Table 1

Compounds of Formula I wherein 1 t ² = phenyl substituted in the para position with R ⁴ :

H

X = F. Y = F. Z = = H. R ¹ = Br. and

El El El El El

OCF ₂ H OCF ₃ OCF ₂ Cl OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br OS(0) ₂ CF ₃

X = F. Y = Cl. Z = H. R ¹ = Br. and

El El El El El

OCF ₂ H OCF ₃ OCF ₂ Cl OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H S(0) ₂ CF ₂ H S(Q) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br OS(0) ₂ CF ₃

X = H. Y = Cl. Z = H. R ¹ = Br. and

El El El El El

OCF ₂ H OCF ₃ 0CF ₂ C1 OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br OS(0) ₂ CF ₃

X = Cl, Y = Cl, 2 : = H. R ¹ = Br, am i

El El El El El

OCF ₂ H OCF ₃ 0CF ₂ C1 OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br OS(0) ₂ CF ₃

X = F, Y = F. Z = = F, R ¹ = Br. and

El El El El El

OCF ₂ H OCF ₃ 0CF ₂ C1 OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ CI S(0) ₂ CF ₂ Br OS(0) ₂ CF ₃

X = H, Y = F. Z = H, R ¹ = I. and

El El El El El

OCF ₂ H OCF ₃ OCF ₂ Cl OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ CI S(Q) ₂ CF ₂ Br OS(Q) ₂ CF ₃

H

X = F, Y = C1. Z = H. R^ I. and

El El El El El

OCF ₂ H OCF ₃ OCF ₂ Cl OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br OS(0) ₂ CF ₃

X = H, Y = Cl, Z - H. R ¹ = 1. and

El El El El El

OCF ₂ H OCF ₃ OCF ₂ CI OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br OS(0) ₂ CF ₃

X = Cl, Y = Cl, i l = W. R ¹ = l. and

El El El El El

OCF ₂ H OCF ₃ OCF ₂ Cl OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ CI S(0) ₂ CF ₂ Br OS(0) ₂ CF ₃

X = F. Y = F. Z = = F. R ¹ = I. and

El El El El El

OCF ₂ H OCF ₃ OCF ₂ Cl OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br OS(0) ₂ CF ₃

F ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ CI SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(Q) ₂ CF ₂ H S(Q) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br OS(Q) ₂ CF ₃

X = F Y = Cl. Z = H. R ¹ = OSfO ^' HMe. and

El El El

OCF ₂ Cl OCF ₂ Br OCF ₂ CF ₂ H SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br OS(0) ₂ CF ₃

X = H, Y = Cl. Z = H. R ¹ = OS(0) ₂ Me, and

El El El El El

OCF ₂ H OCF ₃ 0CF ₂ C1 OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br OS(0) ₂ CF ₃

X = Cl. Y = Cl. 2 : = H. R ^{1 =} OS(0) ₂ Me. and

El El El

OCF ₂ H OCF ₃ OCF ₂ Cl

SCF ₂ H SCF ₃ SCF ₂ CI

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1

S(0) ₂ CF ₂ H S(Q) ₂ CF ₃ S(0) ₂ CF ₂ C1

Table 2 Compounds of Formula I wherein R ² = phenylethynyl substituted in the para position with R$: X = H, Y = F. Z = H. R ¹ = Br. and

E! E! R£

F Cl Br I CN

CF ₃ Me OMe OEt OS(0) ₂ CF ₃

OCF ₂ H OCF ₃ OCF ₂ CI OCF ₂ Br OCF ₂ CF ₂ H SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br S(Q) ₂ CF ₂ CF ₂ H

X = F. Y = Cl. Z = H. R ¹ = Br, and

R5 E! E! R5

F C! Br I CN

CF ₃ Me OMe OEt OS(0) ₂ CF ₃

OCF ₂ H OCF ₃ OCF ₂ Cl OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br S(0) ₂ CF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ CI S(0)CF ₂ Br S(0)CF ₂ CF ₂ H S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ CI S(0) ₂ CF ₂ Br S(0) ₂ CF ₂ CF ₂ H

X = H. Y = F. Z = H. R ¹ = I. and

R5 E! R5 E! E!

F Cl Br I CN

CF ₃ Me OMe OEt 0S(0) ₂ CF ₃

OCF ₂ H OCF ₃ 0CF ₂ C1 OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ CI S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ CI S(0) ₂ CF ₂ Br S(0) ₂ CF ₂ CF ₂ H

X = F. Y = F. Z = = H. R ¹ = I. and

R5 E! E! E!

F Cl Br I CN

CF ₃ Me OMe OEt OS(0) ₂ CF ₃

OCF ₂ H OCF ₃ 0CF ₂ C1 OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br S(0) ₂ CF ₂ CF ₂ H

X = F. Y = C1. Z = H. R ¹ = L and

R5 E£ R5 El

F Cl Br I CN

CF ₃ Me OMe OEt OS(0) ₂ CF ₃

OCF ₂ H OCF ₃ OCF ₂ Cl OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br S(0) ₂ CF ₂ CF ₂ H

I. and

X = F. Y = F. Z = = F. R ¹ =I.and

El El

F Cl

CF ₃ Me

OCF ₂ H 0CF ₃

SCF ₂ H SCF ₃

S(0)CF ₂ H S(0)CF ₃

S(0) ₂ CF ₂ H S(0) ₂ CF ₃

X = F. Y = F. Z = H. R ! = OS(Q) ₂ Me, and

El El

F Cl

CF ₃ Me

OCF ₂ H OCF ₃

SCF ₂ H SCF ₃

S(0)CF ₂ H S(0)CF ₃

S(0) ₂ CF ₂ H S(0) ₂ CF ₃

X - F. Y = Cl. Z = H. R ¹ = OS(Q) Me. and

El

CN

0S(0) ₂ CF ₃

0CF ₂ CF ₂ H

SCF ₂ CF ₂ H

S(0)CF ₂ CF ₂ H S(0) ₂ CF ₂ CF ₂ H

X = H. Y = Cl. Z = ^■ H. R ¹ = OS(Q) ₂ Me. and

El El El El El

F Cl Br I CN

CF ₃ Me OMe OEt OS(0) ₂ CF ₃

OCF ₂ H OCF ₃ OCF ₂ Cl OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br S(0) ₂ CF ₂ CF ₂ H

X = Cl. Y = Cl. 2 : = H. R' = OSfO> ;Me. and

El El El El El

F Cl Br I CN

CF ₃ Me OMe OEt OS(0) ₂ CF ₃

OCF ₂ H OCF ₃ OCF ₂ Cl OCF ₂ Br OCF ₂ CF ₂ H

SCF ₂ H SCF ₃ SCF ₂ C1 SCF ₂ Br SCF ₂ CF ₂ H

S(0)CF ₂ H S(0)CF ₃ S(0)CF ₂ C1 S(0)CF ₂ Br S(0)CF ₂ CF ₂ H

S(0) ₂ CF ₂ H S(0) ₂ CF ₃ S(0) ₂ CF ₂ C1 S(0) ₂ CF ₂ Br S(0) ₂ CF ₂ CF ₂ H

X - F. Y - F. Z = F. R ' = OSfO) ₂ Me. and

El El

F Cl

CF ₃ Me

OCF ₂ H OCF ₃

SCF ₂ H SCF ₃

S(0)CF ₂ H S(0)CF ₃

S(0) ₂ CF ₂ H S(0) ₂ CF ₃

Formulation/Utility

Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.

The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.

Weight Percent

Active Ingredient Diluent Surfactant

Water-Dispersible and Water-soluble 5-90 0-94 1-15 Granules, Tablets and Powders.

Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates)

Dusts 1-25 70-99 0-5

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

High Strength Compositions 90-99 0-10 0-2

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity. Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4- methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration

techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; 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 conventional ways. Compound numbers refer to compounds in Index Tables A-C.

Example A Wettable Powder Compound 4 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%. Example B

Granule

Compound 5 10.0% attapulgite granules (low volatile matter,

0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%. Example C

Extruded Pellet

Compound 4 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alky lnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.

Example D Emulsifiable Concentrate

Compound 5 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.

The compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term "arthropods" includes insects, mites and nematodes) which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests. Nevertheless, all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, juveniles and adults of the Phylum Nematoda. The compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes. Specifically, the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite (Tetranychus urticae), fall armyworm (Spodoptera frugiperdά), black bean aphid (Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypiϊ), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatella furcifera), green leafhopper (Nephotettix cincticeps), brown planthopper (Nilaparvata lugens), small brown planthopper (Laodelphax striatellus), rice stem borer (Chilo suppressalis), rice leafroller (Ct ψhalocrocis medinalis), black rice stink bug (Scotinophara lurida), rice stink bug (Oebalus pugnax), rice bug (Leptocorisa chinensis), slender rice bug (Cletus puntiger), and southern green stink bug (Nezara viridulά). The compounds are active on mites, demonstrating ovicidal, larvicidal and chemosterilant activity against such families as Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus

citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis; Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus californicus and Brevipalpus obovatus; Eriophyidae including Phyllocoptruta oleivora, Eriophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae. See WO 90/10623 and WO 92/00673 for more detailed pest descriptions.

Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of such agricultural protectants with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, beta-cyfluthrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon and triflumuron; fungicides such as azoxystrobin (ICIA5504), benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromuconazole, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cymoxanil, cyproconazole, cyprodinil (CGA 219417), diclomezine, dicloran, difenoconazole, dimethomorph, diniconazole, diniconazole-M, dodine, edifenphos, epoxiconazole (BAS 480F), fenarimol, fenbuconazole, fenpiclonil, fenpropidin, fenpropimorph, fiuquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl (BAS 490F), mancozeb, maneb, mepronil, metalaxyl, metconazole, myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propiconazole, pyrifenox, pyroquilon, sulfur, tebuconazole, tetraconazole, thiabendazole, thiophanate-methyl, thiram, triadimefon, triadimenol, tricyclazole, triticonazole, uniconazole, validamycin and vinclozolin; nematocides such as aldoxycarb and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as

Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.

In certain instances, combinations with other arthropodicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.

Preferred for better control of pests (use rate or spectrum) or resistance management are mixtures of a compound of this invention with an arthropodicide selected from the group abamectin, fenpropathrin, fipronil, imidacloprid, methomyl, propargite, pyridaben, tebufenozide and tebufenpyrad. Specifically preferred mixtures (compound numbers refer to compounds in Index Tables A-C) are selected from the group: compound 3 and abamectin; compound 3 and fenpropathrin; compound 3 and fipronil; compound 3 and imidacloprid; compound 3 and methomyl; compound 3 and propargite; compound 3 and pyridaben; compound 3 and tebufenozide; compound 3 and tebufenpyrad; compound 4 and abamectin; compound 4 and fenpropathrin; compound 4 and fipronil; compound 4 and imidacloprid; compound 4 and methomyl; compound 4 and propargite; compound 4 and pyridaben; compound 4 and tebufenozide; compound 4 and tebufenpyrad; compound 5 and abamectin; compound 5 and fenpropathrin; compound 5 and fipronil; compound 5 and imidacloprid; compound 5 and methomyl; compound 5 and propargite; compound 5 and pyridaben; compound 5 and tebufenozide; and compound 5 and tebufenpyrad.

Arthropod pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Thus, the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or more of the compounds of the invention, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. A preferred method of application is by spraying. Alternatively, granular formulations of these compounds can be applied to the plant foliage or the soil. Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like.

The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy.

The rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.

The following TESTS demonstrate the control efficacy of compounds of this invention on specific pests. "Control efficacy" represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-C for compound descriptions. The following abbreviations are used in the Index Tables which follow: Me = methyl, and S(O) ₂ Me = methylsulfonyl. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared. INDEX TABLE A

Cmod No. X Y Z El El m.p. CC)

1 F F H Br OCF ₃ 140-141

2 F F H I OCF ₃ 150- 151

3 (Ex. 1 ) F F H Br SCF ₂ H 129- 130

4 F F H OS(0) ₂ Me SCF ₂ H 198-200

5 (Ex. 2) F F H I SCF ₂ H 132-137

6 F F H 1 SCF ₃ 132-135

7 F F H Br SCF ₃ oil*

8 F F H OS(0) ₂ Me SCF ₃ oil* oa F F H 0S(O) ₂ Me OCF ₃ 98-100* ^a Compound contains approximately 35% by weight of 2-(2,6-difluorophenyl)-4,5- dihydro-4-[4'-(trifluoromethoxy)[l,r-biphenyl]-4-yl]oxazole by 'H NMR analysis. *See Index Table C for ^l H NMR data.

INDEX TABLE B

CmDd No. X Y Z El El m.p. (°C)

10 F F H I F 148-160

1 1 (Ex. 4) F F H OS(0) ₂ Me F 135-137

12 (Ex. 3) F F H Br F 163-164

13 F F H I OCF ₂ H 163-165

14 F F H OS(0) ₂ Me OCF ₂ H 120-125

INDEX TABLE C

Cmpd No. 'H NMR Data (CDC1 ₃ solution unless indicated otherwise) ³

7 δ 3.b0-3.88 (m,2H), 5.62 (m,lH), 6.62 (d,lH), 7.00 (m,2H), 7.32-7.80 (m,9H).

8 δ 3.00 (s,3H), 4.54-4.68 (m,2H), 5.62 (m,lH), 6.80-7.80 (m,12H).

9 δ 2.99 (s,3H), 4.54-4.68 (m,2H), 5.60 (m,lH), 6.90 (m,lH), 7.20-7.60 (m,l IH) plus approximately 35% by weight of the oxazole showing peaks at 4.34 (m,lH), 4.82 (m,lH), 5.54 (m,lH), 7.04 (m,2H), 7.26 (m,2H), 7.41 (m,3H), 7.58 (m,4H).

^{a ]} H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br s)-broad singlet.

BIOLOGICAL EXAMPLES OF THE INVENTION TEST A Fall Armyworm Test units, each consisting of a H.I.S. (high impact styrene) tray with 16 cells were-prepared. Wet filter paper and approximately 8 cm ² of lima bean leaf was placed into twelve of the cells. A 0.5-cm layer of wheat germ diet was placed into the four remaining cells. Fifteen to twenty third-instar larvae of fall armyworm (Spodoptera frugiperdd) were placed into a 230-mL (8-ounce) plastic cup. Solutions of each of the test compounds in 75:25 acetone-distilled water solvent were sprayed into the tray and cup. Spraying was accomplished by passing the tray and cup on a conveyer belt directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.138 kilograms of active ingredient per hectare (about 0.13 pounds per acre) at 207 kPa (30 p.s.i.). The insects were transferred from the 230-mL cup to the H.I.S. tray (one insect per cell). The trays were covered and held at 27°C and 50% relative humidity for 48 hours, after which time readings were taken on the twelve cells with lima bean leaves. The four remaining cells were read at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 12.

TEST B Two-Spotted Spider Mite

Pieces of kidney bean leaves, each approximately 6.5 cm ² (1 square inch) in area, that had been infested on the undersides with 25 to 30 adult mites (Tetranychus urticae), were sprayed with their undersides facing up on a hydraulic sprayer with a solution of the test compound in 75:25 acetone-distilled water solvent. Spraying was accomplished by passing the leaves, on a conveyor belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.138 kilograms of active ingredient per hectare (about 0.13 pounds per acre) at 207 kPa (30 p.s.i.). The leaf squares were then placed underside-up on a square of wet cotton in a petri dish and the perimeter of the leaf square was tamped down onto the cotton with forceps so that the mites could not escape onto the untreated leaf surface. The test units were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher:

The same units were held an additional 5 days and read for larvicide/ovicide mortality and/or developmental effects. Of the compounds tested, the following gave activity levels of 80% or higher: 1, 2 and 12.

TEST C Larval two-Spotted Spider Mites (Tetranychus urticae)

Solutions of the test compounds were prepared by dissolving in a minimum of acetone and then adding water containing a wetting agent until the concentration of the compound was 5 ppm. Two-week old red kidney bean plants infested with two-spotted spider mites eggs were sprayed to run-off (equivalent to 2.8 g/ha) with the test solution using a turntable sprayer. Plants were held in a chamber at 25°C and 50% relative humidity. Of the compounds tested, the following gave larvicide/ovicide activity of 80% or higher seven days after spraying: 1, 2, 3, 4, 5, 6, 7, 10, 1 1, 12 and 13. TEST D

Fall Armyworm Whole Plant Test

Solutions of the test compounds were prepared by dissolving in a minimum of acetone and adding water containing a wetting agent until the concentration of the compounds was 10 ppm. Test compounds were then sprayed to run-off (equivalent to 5.5 g/ha) onto soybean plants utilizing a rotating platform and an atomizing sprayer. Treated plants were dried, and fall armyworm (Spodoptera frugiperdά) larvae were exposed to excised, treated leaves. Test units were held at 27°C and 50%o relative humidity, and evaluated for larval mortality 120 h post-infestation. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 2, 3, 10, 11 and 12.