WO1991012228A1

WO1991012228A1 - Arthropodicidal trichloromethylbenzylamines

Info

Publication number: WO1991012228A1
Application number: PCT/US1991/000371
Authority: WO
Inventors: Mohamed Abdel Hamid +Di Fahmy
Original assignee: E.I. Du Pont De Nemours And Company; Fahmy, Salwa +Ef
Priority date: 1990-02-09
Filing date: 1991-01-24
Publication date: 1991-08-22
Also published as: EP0515525A1; CA2075382A1; JPH05504569A

Abstract

Certain benzylamines having formula (I), wherein Q, R, R1 and R2 are as defined herein; compositions containing them and their use as arthropodicides for both agricultural and home applications.

Description

TITLE

ARTHROPODICIDAL TRICHLOROMETHYLBENZYLAMINES

FIELD OF THE INVENTION

Trichloromethylbenzylamines useful as

arthropodicides, compositions containing them and methods for using them.

STATE OF THE ART

DD 123049 discloses N-(benzyl) amines as plant growth regulators. Div. Agric. Chem.; Ind. Agric.

Res. Inst. Ind. J. Chem., Sect. B 16B(3), 250 to 252, discloses the preparation of 2-(trichloromethylbenzyl)anilines. J. Agric. Food Chem.; 24(4) 724 to

727, 1976, discloses N-(α-CCl₃benzyl)aniline).

JP 49/101526 and DE 2,301,397 disclose

α-(cci₃benzyl) aniline insecticides. J. Agr. Food Chem., 20(4) 818 to 824, 1972, discloses

α-(CCl₃benzyl) anilines and phenylethers with DDT-like activity.

SUMMARY OF THE INVENTION

The invention pertains to compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use as

arthropodicides in both agronomic and nonagronomic environments. The compounds are:

wherein

Q is selected from the group

R is selected from the group H, C₁-C₃ alkyl, CHO, C₂-C₅ alkylcarbonyl, C₂-C₄

haloalkylcarbonyl, benzyl optionally substituted by W, C₂-C₅ alkoxycarbonyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl and SR₅;

R₁ is selected from the group halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₃-C₄ alkenyloxy, C₃-C₄ alkynyloxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ haloalkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, NO₂ and CN;

R₂ is selected from the group H, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄ alkenyloxy, C₂-C₄ alkynyloxy, C₂-C₄ alkenyl, C₂-C₄

haloalkenyl, C₂-C₄ alkynyl, C₂-C₄

alkoxycarbonyl, C₁-C₄ alkylamino, di-C₁-C₄ alkylamino, NO₂ and CN;

R₃ and X are independently selected from the group H, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄ alkoxycarbonyl, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ haloalkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, NO₂ and CN; R₄ is selected from the group H, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy and CN;

R₅ is selected from the group CCl₃, N(R₆)COR₇, phenyl optionally substituted with W, and benzyl optionally substituted with W;

W is selected from the group halogen, CF₃,

OCF₃, C₁-C₄ alkyl, nitro, and C₁-C₄ alkoxycarbonyl;

R_x is selected from the group H and halogen; R₆ is selected from the group C₁-C₄ alkyl; and R₇ is selected from the group C₁-C₄ alkyl.

Preferred Compounds A are those of Formula I wherein R₁ is in the para position and R is H.

Preferred Compounds B are those of Preferred A wherein Q is Q-1.

Preferred Compounds C are those of Preferred A wherein Q is Q-2.

Preferred Compounds D are those of Preferred C wherein R₁ is selected from the group F, Cl, Br, CF₃, OCH₂C≡CH, OCHF₂ and OCF₃. In the above recitations, the term "alkyl", used either alone or in compound words such as

"alkythio" or haloalkyl", denotes straight chain or branched alkyl such as methyl, ethyl, n-propyl, isopropyl or the different butyl isomers. Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy isomers. Alkenyl denotes straight chain or branched alkenes such as vinyl,

1-propenyl, 2-proρenyl, 2-propenyl and the different butenyl isomers. Alkynyl denotes straight chain or branched alkynes such as ethynyl, 1-proρynyl,

3-propynyl and the different butynyl isomers.

Alkylthio denotes methylthio, ethylthio and the different propylthio and butylthio isomers.

Alkylsulfinyl, alkylsulfonyl, alkylamino, etc., are defined analogously to the above examples.

The term "halogen", either alone or in compound words such as "haloalkyl", denotes fluorine,

chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl can be partially or fully substituted with halogen atoms, which can be the same or different. Examples of haloalkyl include CH₂CH₂F, CF₂CF₃ and CH₂CHFCl. The terms "haloalkylthio" haloalkenyl" and "haloalkoxy" are defined analogously to the term "haloalkyl".

The total number of carbon atoms in a

substituent group is indicated by the "C_i-C_j" prefix where i and j are numbers from 1 to 5. For example, C₁-C₃ alkysulfonyl designates methylsulfonyl through propylsulfonyl; C₂ alkylcarbonyl designates C(O)CH₃ and C₄ alkylcarbonyl includes C(O)CH₂CH₂CH₃ and

C(O)CH(CH₃)₂; and as a final example, C₃

alkoxycarbonyl designates CO₂CH₂CH₃ and C₄

alkoxycarbonyl includes CO₂CH₂CH₂CH₃ and CO₂CH(CH₃)₂. DETAILS OF THE INVENTION

Compounds of Formula I can be prepared by various methods. One reaction sequence is the formation of an imine from a desired aryl or

heteroaryl amine by reaction with an appropriate aldehyde by conventional methods as illustrated in Scheme 1.

SCHEME 1

Imines of Scheme 1 can further react with

trichloroacetic acid according to procedures

described by Hirwe et al. , J. Ag. Food Chem. 20, 818 to 24, 1972 and Yost et al. , J. Ag. Food Chem. , 24, 724 to 727, 1976 to give compounds of Formula I as shown in Scheme 2.

SCHEME 2

The addition of the trichloromethyl group to imines can be accomplished by other methods to form compounds of Formula I. One such method is the addition of chloroform to imines under basic conditions in an aprotic solvent such as

dimethylformamide in a manner similar to the synthesis of α-trichloromethylbenzyl carbinols from aldehydes (Wyvratt et al , J. Org. Chem. 52, 944, 1987). This method is illustrated in Scheme 3.

SCHEME 3

Alternatively, the addition of the trichloromethyl group to imines can be accomplished through the utilization of trichloromethyl lithium as shown in Scheme 4.

SCHEME 4

The trichloromethyl lithium reagent is prepared from chloroform and butyl lithium as described by

Kόbrich, G. et al. , Angew. Chem. , 76,536 (1964).

Compounds of Formula I where R is other than hydrogen can be prepared by reaction of the

corresponding imine of Scheme 1 with R-X (wherein X is a leaving group) followed by the reaction of the resulting iminium salt with trichloromethyl lithium in a manner similar to a procedure described by Brook et al. , Syn. Commun. 18., 893 to 898 (1988) for the reaction of imines with trimethylsilyl triflate followed by the addition of nucleophiles and as illustrated in Scheme 5.

SCHEME 5

Compounds of Formula I (where R is SR₅) can be prepared from compounds of Formula I by reaction with the appropriate ClSR₅ in the presence of a base such as a tertiary amine as shown in Scheme 6. SCHEME 6

Sulfenyl halides of the type ClSR₅ wherein R₅ is as specified in this disclosure are known in the

literature. A review article by Englebert Kuhle

(Synthesis , 561 (1970)) describes the chemistry and the preparation of the majority of sulfenyl halides utilized in this invention. The synthesis of

N-chlorosulfenylcarbamates is described in U.S.

3,843,689.

The following Examples illustrate the invention.

EXAMPLE 1

N-(4-Chloro-α-trichloromethylbenzyl)-3,5- bis(trifluoromethyl)aniline (1)

To a solution of 4-chlorobenzaldehyde (2.8 g, 0.02 mol) in 20 ml of toluene was added

3,5-bis(trifluoromethyl) aniline (4.6 g, 0.02 mol).

Molecular sieves 5A (20 g) were added to the mixture and stirred at room temperature overnight. The sieves were filtered and washed with CH₂Cl₂ (2 x 50 ml) and the solvents were evaporated under vacuum, to give N-(4-chlorobenzylidene)-3,5-bis(trifluoromethyl) aniline (IA). The product was a solid; mp 55-57°C. Then, 3.3 g (0.01 mol) of 1A was mixed with trichloroacetic acid (2.0 g, 0.012 mol) and heated slowly to 120°C under a nitrogen atmosphere. The temperature was maintained between 120 to 125°C until gas evolution ceased. The reaction was cooled to room temperature and 100 ml of CH₂Cl₂ was added. The solution was washed with 10% sodium carbonate (2 x 20 ml), then with water (2 x 20 ml) and dried over anhydrous MgSO₄. Evaporation of the solvent followed by chromatography on silica gel (hexane) gave 1; mp 81° to 83°C. ¹H-NMR spectrum of 1 in CDCI3 showed the following chemical shifts (in ppm) : δ 7.54 (d, 2H), 7.38 (d, 2H), 7.24 (m, 1H), 7.0 (m, 2H), 5.12 and 5.13 (s, 2H).

2-(4-Chloro-α-trichloromethylbenzylamino)- 3,5-dichloropyridine (2 )

To a solution of 2-amino-3, 5-dichloropyridine

(9.9 g, 0.06 mol) in 60 ml of CH₂Cl₂ was added

4-chlorobenzaldehyde (8.4 g, 0.06 mol) followed by 60 g of molecular sieves 5A. The mixture was stirred at room temperature for three days. The reaction mixture was filtered and the sieves were washed with CH₂Cl₂ (5 x 50 ml). The solvent was evaporated under vacuum to give 2-(N-4-chlorobenzylidene)amino- 3,5-dichloropyridine (2A) as a solid; mp 101-103°C.

Then, 15.0 g 2A (0.053 mol) was mixed with trichloroacetic acid (25 g, 0.153 mol) under a nitrogen atmosphere. The mixture was heated slowly up to 132°C and maintained at this temperature for two hours until gas evolution ceased. The mixture was cooled to room temperature and CH₂Cl₂ (300 ml) was added. The solution was washed with 10% sodium bicarbonate solution (2 x 100 ml), then with water (2 x 20 ml), and the organic phase was dried over MgSO₄. The solvent was evaporated under vacuum and the residue was chromatographed on silica gel

(hexane) to give 2 as a solid; mp 105° to 108°C.

1H-NMR spectrum of 2 in CDCl₃ showed the following chemical shifts (in ppm): δ 7.95 (m, 1H), 7.53 (m, 3H), 7.35 (d, 2H), 6.24 (d, 1H), 6.05 (d, 1H).

EXAMPLE 3

N-(4-chloro-α-trichloromethylbenzyl)-N-

[(N'-butoxycarbonyl-N'-methyl)amino sulfenyl]- 3,5-bis(trifluoromethyl)aniline (3) To a cold solution (0°C) of N-(4-chloro-α- trichloromethylbenzyl)-3,5-bis(trifluoromethyl)- aniline (1.0 g, 2.6 mmol, from Example 1) in 10 ml CH₂Cl₂ was added triethylamine (0.6 g, 6 mmol).

Butyl (chlorosulfenyl) (methyl)carbamate (1.2 g, 6 mmol) was added dropwise with stirring at 0°C.

After complete addition of the carbamate, the

temperature was allowed to rise to room temperature and stirring was continued overnight. The solvent was evaporated under vacuum and the residue was chromatographed on silica gel column (hexane) to give (3) as a viscous oil. ¹H-NMR of 3 in CDCI₃ showed the characteristic chemical shift (in ppm) of S 3.58 (S, 3H) for NSNCH₃.

EXAMPLE 4

3,5-Dichloro-N-(2,2,2-trichloro-1-(4-(1,3-dioxolan- 2-yl)phenyl)ethyl)-2-pyridinamine ( 4 )

Step A: 3,5-Dichloro-N-(2,2,2-trichloroethylidene)- 2-pyridinamine

To a solution of 2-amino-3,5-dichloropyridine (16.3 g, 0.10 mole) in 125 ml of chlorobutane was added 5A molecular sieves (20g). At 0°C, anhydrous chloral (15 g, 0.10 mol) was added dropwise, and the mixture was allowed to warm to room temperature and to stir overnight.

The reaction mixture was filtered through

Celite and the sieves were washed with chlorobutane. The filtered solution was cooled in an ice bath, and thionyl chloride (35.5 g, 0.30 mol) was added

dropwise. The resulting white suspension was then heated to reflux for six hours, producing a clear solution. The excess thionyl chloride was evaporated under vacuum, and the residue was dissolved in 150 ml of ethyl ether. To this solution was added

triethylamine (12.1 g, 0.12 mol) at 0°C, producing a white precipitate. After 15 minutes, this mixture was filtered and the filter cake was washed with hexanes. The filtrate was concentrated under vacuum to give the imine 4A as a brown solid, 23.67 g. The ¹H NMR spectrum of this compound in CDCl₃ showed the following chemical shifts (in ppm): δ 8.59 (s, 1H), 8.35 (fine d, 1H), 7.85 (fine d, 1H).

Step B: To a solution of 4-bromobenzaldehyde (5.55 g, 30 mmol) in 25 ml of toluene was added ethylene glycol (2.23 g, 36 mmol) and p-toluenesulfonic acid monohydrate (0.27 g, 1.4 mmol). This mixture was stirred under nitrogen and heated overnight with azeotropic removal of water. The reaction mixture was washed with saturated aqueous sodium bicarbonate solution, then with water and with brine solution. The organic phase was dried over MgSO₄ and filtered. The solvent was evaporated under vacuum.

The residue (2.29 g, 10 mmol) was then

dissolved in 30 ml of tetrahydrofuran and cooled to -70°C. A solution of n-BuLi (4.40 ml of a 2.5 M solution in hexanes, 11 mmol) was then added

dropwise. Solid magnesium bromide etherate (3.10 g, 12 mmol) was then added in one portion, and the mixture was stirred for 30 minutes at -70°C. A solution of the compound from Step A (2.63 g, 9.0 mmol) in 5 ml of tetrahydrofuran was then added dropwise. The reaction mixture was stirred at low temperature for 30 minutes, and 0.6 ml of glacial acetic acid was added. At room temperature, the reaction mixture was diluted with an equal amount of ether and washed with saturated aqueous sodium bicarbonate, water, and brine. The organic phase was dried over MgSO₄ and filtered, and the solvent was removed under vacuum.

The residue was chromatographed on silica gel with 10% ethyl acetate/hexane to give 4. as a viscous oil, 2.14 g.

1H NMR spectrum of 4 in CDCl₃ showed the following chemical shifts (in ppm): δ 7.96 (fine d, 1H), 7.63 (d, 2H), 7.47-7.52 (m, 3H), 7.38 (m, 1H), 6.29 (d, 1H), 6.07 (d, 1H), 5.81 (s, 1H), 4.00-4.12 (m, 4H).

EXAMPLE 5

3,5-Dichloro-N-(2,2,2-trichloro-1- (4-cyanophenyl)ethyl)-2-pyridinamine (5)

To a solution of the compound from Example 4 (1.00 g, 2.26 mmol) in 30 ml of acetone was added p-toluenesulfonic acid (0.03 g, 0.15 mmol). This solution was stirred at room temperature overnight. The solvent was removed under vacuum. The residue was dissolved in ether/ethyl acetate and was washed with aqueous sodium bicarbonate, water, and brine. The organic phase was dried over MgSO₄ and the solvent was removed under vacuum. The resultant oil crystallized on standing. The εrolid was triturated with hexane, filtered, and dried to obtain 0.55 g of a white solid (compound 30, mp 152-155°C).

A mixture of the above intermediate (0.29 g, 0.73 mmol) and hydroxylamine hydrochloride (0.12 g , 1.7 mmol) in 5 ml of 96% formic acid was heated at reflux for 3.5 to 4 hours, cooled to room

temperature, and poured over ice. Ether was added, and the mixture was made basic with IN NaOH. The layers were separated, and the organic phase was washed with water and with brine, and dried with MgSO₄. The solvent was removed under vacuum, and the residue was chromatographed in silica gel (5% ethyl acetate/hexane) to afford compound 5; mp 175-176°C.

EXAMPLE 6

3,5-Dichloro-N-(2,2,2-trichloro-1-

(2,4-dichlorophenyl)ethyl)-2-pyridinamine (6) To a solution of 2,4-dichlorobenzaldehyde (8.68 g, 50 mmol) in 65 ml of toluene was added

2-amino-3,5-dichloropiridine (8.08 g, 50 mm01) followed by 50 g of molecular sieves 5A. This mixture was stirred overnight and then filtered through Celite. The filter cake was washed with a 50:50 mixture of CH₂Cl₂/hexane. The solvents were evaporated under vacuum to afford 5.64 g of

2-(N-2,4-dichlorobenzylidene)amino-3,5-dichloropyridine (6A). An additional 8.83 g of this

intermediate was obtained by washing the filter cake with CH₂Cl₂ and concentrating the filtrate under vacuum.

To a cold (-70°C) solution of 6A (0.96 g, 3.0 mmol) in 30 ml of tetrahydrofuran was added a solution of lithium diisopropylamide in

heptane/tetrahydrofuran (4.30 ml of 2.1 M solution, 9.0 mmol). A solution of CHCl₃ (1.49 g, 12.5 mmol) in 5 ml of tetrahydrofuran was then added dropwise over a 15 minute period. A solution of acetic acid (0.6 ml, 10 mmol) in 3 ml of ether was added. At room temperature, the reaction mixture was diluted with ether and washed with saturated aqueous

bicarbonate, water, and brine. The organic phase was dried over MgSO₄, and the solvents were evaporated under vacuum. The residue was chromatographed on silica gel with hexane to afford 0.48 g of 6 as a viscous oil. The ¹H NMR spectrum of this compound in CDCI₃ showed the following chemical shifts (in ppm): δ 8.01 (d, 1H), 7.65 (d, 1H), 7.52 (d, 1H), 7.46 (d, 1H), 7.29 (dd, 1H), 6.88 (d, 1H), 6.04 (d, 1H).

By the general procedures described herein, or obvious modifications thereof, the compounds of Table 1 can be prepared.

KEY FOR TABLE 1

Group R₃

a 2-F

b 2-Br

c 2-CN

d 3-F

e 3-C1

f 3-Br

g 3-CN

h 3-NO₂

i 3-OCH₃

j 3-OCHF₂

k 3-SCH3

l 4-Cl

m 4-CN Compounds of Table 1 wherein R, R₁ and R₂ are as set out therein can be prepared having the recited values of Groups a through m. That is for each value of R, R₁ and R₂ in Table 1, R₃ can be F, Br, CN, Cl, NO₂, OCH₃, OCHF₂ or SCH₃. All of said compounds are specifically included within the scope of this invention. TABLE 1 This Table contains a large number of compounds of Formula I in a format adopted to avoid mechanical reproduction of substituent values that do not vary. For example, the first table entry (where R is H, R₁ is 4-F and R₂ is H) actually specifies 13 separate and distinct compounds because the Key for Table 1 identifies additional substituent values of R₃, namely Group a through m for each Table 1 entry.

KEY FOR TABLE 2

Croup R₃ R⁴ R_x

a 3-Cl 5-Cl H

b 3-Br 5-Br H

c 3-Cl 5-CF3 H

d 3-CF3 5-CF3 H

e 4-CF3 6-CF3 H

f 3-Cl 6-CF3 H

g 4-Cl 6-CF3 H

h 5-Cl 6-CF3 H

i 3-CN 5-Cl H

j 3-CN 6-Cl H

k 3-C1 5-CN H

l 3-CN 5-CF₃ H

m 3-CN 6-CF₃ H

n 5-CN 6-CF3 H

o 5-CN CH₃ CH₃

p 3-Cl 5-CF₃ H

Compounds of Table 2 wherein R, R₁ and R₂ are as set out therein can be prepared having the recited values of Groups a through p. That is, for each value of R, R₁ and R₂, R₃, R₄ and R_x can be H, Cl, Br, CH₃, CF₃ or CN. All of said compounds are specifically included within the scope of this invention.

TABLE 2

This Table contains a large number of compounds of Formula I in a format adopted to avoid mechanical reproduction of substituent values that do not vary. For example, the first table entry (where R is H, R₁ is 4-F and R₂ is H) actually specifies 16 separate and distinct compounds because the Key for Table 2 identifies additional substituent values of R₃, R₄ and R_x, namely Groups a through p for each Table 2 entry.

KEY FOR TABLE 3

Group R₃ R₄

a 2-CF₃ 6-CF3

b 2-Cl 6-Cl

c 3-Cl 5-Cl

d 2-F 6-F

e 2-CH, 6-CH₃

Compounds of Table 3 wherein R, R₁ and R₂ are as set out therein can be prepared having the recited values of Groups a through e. That is, for each value of R, R₁ and R₂, R₃ and R₄ can be CF₃, Cl, F or CH₃. All of said compounds are specifically included within the scope of this invention.

TABLE 3

This Table contains a large number of compounds of Formula I in a format adopted to avoid mechanical reproduction of substituent values that do not vary. For example, the first table entry (where R is H, R₁ is 4-F and R₂ is H) actually specifies 5 separate and distinct compounds because the Key for Table 3 identifies additional substituent values of R₃ and R₄, namely Groups a through e for each Table 3 entry.

Formulation and Use

The compounds of this invention will generally be used in formulation with an agriculturally

suitable carrier comprising a liquid or solid diluent or an organic solvent. Useful formulations of the compounds of Formula I can be prepared in

conventional ways. They include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry

flowables and the like. Many of these can be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from

about one to several hundred liters per hectare.

High strength compositions are primarily used as

intermediates for further formulation. The

formulations, broadly, contain from less than about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain effective amounts of these ingredients in the following approximate

proportions:

Percent by Weight

Active

Ingredient Diluent(s) Surfactant(s)

Wettable Powders 25-90 0-74 1-10

Oil Suspensions, 5-50 40-95 0-15

Emulsions, Solutions,

(including Emulsifiable

Concentrates)

Dusts 1-25 70-99 0-5

Granules, Baits 0.01-95 5-99 0-15

and Pellets

High Strength 90-99 0-10 0-2

Compositions Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New

Jersey. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C.

"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, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, U.S. 3,060,084). Granules and pellets can be made by spraying the active

material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning,

"Agglomeration", Chemical Engineering, December 4, 1967, pages 147 and following, and "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 59 and following.

Example A

Emulsifiable Concentrate

N-(4-chloro-α-trichloromethylbenzyl)-3,5-bis

(trifluoromethyl) aniline 20%

blend of oil soluble sulfonates

and polyoxyethylene ethers 10% isophorone 70%

The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product.

Example B

Wettable Powder

N-(4-chloro-α-trichloromethylbenzyl)-3,5-bis

(trifluoromethyl) aniline 30%

sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 63%

The active ingredient is mixed with the inert materials in a blender. After grinding in a hammer- mill, the material is re-blended and sifted through a 50 mesh screen.

Example C

Dust

Wettable powder of Example B 10% pyrophyllite (powder) 90% The wettable powder and the pyrophyllite diluent are thoroughly blended and then packaged. The product is suitable for use as a dust.

Example D

Granule

N-(4-chloro-α-trichloromethylbenzyl)-3,5-bis

(trifluoromethyl) aniline 10%

attapulgite granules (low volative

matter, 0.71/0.30 mm; U.S.S. No.

25-50 sieves) 90%

The active ingredient is dissolved in a volatile solvent such as acetone and sprayed upon dedusted and pre-warmed attapulgite granules in a double cone blender. The acetone is then driven off by heating. The granules are then allowed to cool and are packaged. Example E

Granule

Wettable powder of Example B 15%

gypsum 69%

potassium sulfate 16%

The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 0.1 to 0.42 mm (U.S.S. No. 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain 4.5% active ingredient.

Example F

Solution

N-(4-chloro-α-trichloromethylbenzyl)-3,5-bis

(trifluoromethyl) aniline 25% N-methyl-pyrrolidone 75%

The ingredients are combined and stirred to produce a solution suitable for direct, low volume application.

Example G

Aoueous Suspension

N-(4-chloro-α-trichloromethylbenzyl)-3,5-bis

(trifluoromethyl) aniline 40%

polyacrylic acid thickener 0.3% dodecyclophenol polyethylene glycol

ether 0.5% disodium phosphate 1.0% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7%

The ingredients are blended and ground together in a sand mill to produce particles substantially all under 5 microns in size.

Example H

Oil Suspension

N-(4-chloro-α-trichloromethylbenzyl)-3,5-bis

(trifluoromethyl) aniline 35.0%

blend of polyalcohol carboxylic 6.0% esters and oil soluble petroleum

sulfonates

xylene range solvent 59.0%

The ingredients are combined and ground together in a sand mill to produce particles substantially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water. Example I

Bait Granules

N-(4-chloro-α-trichloromethylbenzyl)-3,5-bis

(trifluoromethyl) aniline 3.0% blend of polyethoxylated nonyl- 9.0% phenols and sodium dodecyl- benzene sulfonates

ground up corn cobs 88.0%

The active ingredient and surfactant blend are dissolved in a suitable solvent such as acetone and sprayed onto the ground corn cobs. The granules are then dried and packaged.

Compounds of Formula I can also be mixed with one or more other insecticides, fungicides,

nematocides, bactericides, acaricides, or other biologically active compounds to form a

multi-component pesticide giving an even broader spectrum of effective agricultural protection.

Examples of other agricultural protectants

with which compounds of this invention can be

formulated are: Insecticides:

3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester

(monocrotophos)

methylcarbamic acid, ester with 2,3-dihydro-2,2- dimethyl-7-benzofuranol (carbofuran)

O-[2,4,5-trichloro-α-(chloromethyl)benzyl]phosphoric acid, O',O'-dimethyl ester (tetrachlorvinphos) 2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl parathion) methylcarbamic acid, ester with α-naphthol (carbaryl) methyl O-(methylcarbamoyl)thiolacetohydroxamate

(methomyl)

N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine

(chlordimeform)

O,O-diethyl-O-(2-isopropyl-4-methyl-6-ρyrimidylρhosphorothioate (diazinon)

octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN) (S)-a-cyano-m-phenoxybenzyl(1R,3R)-3-(2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate (deltamethrin) Methyl-N',N'-dimethyl-N-[(methylcarbamoyl)oxy]-1- thioox amimidate (oxamyl)

cyano(3-phenoxyphenyl)-methyl-4-chloro-a-(1-methylethyl)benzeneacetate (fenvalerate)

(3-phenoxyρhenyl)methyl(±)-cis,trans-3-(2,2-dichloro ethenyl)-2,2-dimethylcyclopropanecarboxylate (permethrin)

a-cyano-3-ρhenoxybenzyl 3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropane carboxylate (cypermethrin)

O-ethyl-S-(p-chlorophenyl)ethylphosρhonodithioate

(profenofos)

phosphorothiolothionic acid,

O-ethyl-O-[4-(methylthio)-phenyl]-S-n-propyl ester

(sulprofos).

Additional insecticides are listed hereafter by their common names: triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fonophos, isofenphos, methidathion, methamidiphos, monocrotphos, phosmet, phosphamidon, phosalone, pirimicarb, phorate,

profenofos, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, metaldehyde and rotenone.

Fungicides:

methyl 2-benzimidazolecarbamate (carbendazim)

tetramethylthiuram disulfide (thiuram)

n-dodecylguanidine acetate (dodine)

manganese ethylenebisdithiocarbamate (maneb)

1,4-dichloro-2,5-dimethoxybenzene (chloroneb)

methyl 1-(butylcarbamoly)-2-benzimidazolecarbamate

(benomyl)

1-[2-(2,4-dichloroρhenyl)-4-propyl-1,3-dioxolan-2- ylmethyl]-1H-1,2,4-triazole (propiconazole)

2-cyano-N-ethylcarbamoy-2-methoxyiminoacetamide

(cymoxanil)

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1- yl)-2-butanone (triadimefon)

N-(trichloromethylthio)tetrahydrophthalimide (captan)

N-(trichloromethylthio)phthalimide (folpet)

1-[[[bis(4-fluorophenyl)][methyl]siIyl]methyl]-1H-

1,2,4-triazole. Nematicides:

S-methyl 1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)- thioformimidate

S-methyl

1-carbamoyl-N-(methylcarbamoyloxy) thioformimidate

N-isopropylphosphorarnidic acid, O-ethyl

O'-[4-(methylthio)-m-tolyl] diester (fenamiphos)

Bactericides:

tribasic copper sulfate

streptomycin sulfate Acaricides:

senecioic acid, ester with 2-sec-butyl-4,6-dinitro- phenol (binapacryl)

6-methyl-1,3-cithiolo[4,5-β]quinoxalin-2-one

(oxythioquinox)

ethyl 4,4'-dichlorobenzilate (chlorobenzilate)

1,1-bis(p-chlorophenyl)-2 , 2,2-trichloroethanol

(dicofol)

bis(pentachloro-2,4-cyclopentadien-1-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin)

trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxo- thiazolidine-3-carboxamide (hexythiazox)

amitraz

propargite

fenbutatin-oxide

Biological

Bacillus thuringiensis

Avermectin B.

Utility

The compounds of this invention exhibit activity against a wide spectrum of foliar and soil inhabiting arthropods 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 recognize that not all compounds are equally effective against all pests but the compounds of this invention display activity against economically important agronomic, forestry, greenhouse, ornamental food and fiber product, stored product, domestic structure, and nursery pests, such as: larvae of the order Lepidoptera including fall and beet armyworm and other Spodoptera spp., tobacco budworm, corn earworm and other

Heliothis spp.. European corn borer, navel orangeworm, stalk/stem borers and other pyralids, cabbage and soybean loopers and other loopers, codling moth, grape berry moth and other tortricids, black cutworm, spotted cutworm, other cutworms and other noctuids, diamondback moth, green cloverworm,

velvetbean caterpillar, green cloverworm, pink bollworm, gypsy moth, and spruce budworm; foliar feeding larvae and adults of the order Coleoptera including Colorado potato beetle, Mexican bean beetle, flea beetle, Japanese beetles, and other leaf beetles, boll weevil, rice water weevil, granary weevil, rice weevil and other weevil pests, and soil inhabiting insects such as Western corn rootworm and other Diabrotica spp., Japanese beetle, European chafer and other coleopteran grubs, and wireworms; adults and larvae of the orders Hemiptera and Homoptera including tarnished plant bug and other plant bugs (miridae), aster leafhopper and other leafhoppers (cicadellidae), rice planthopper, brown planthopper, and other planthoppers (fulooroidea), psylids,

whiteflies (aleurodidae), aphids (aphidae), scales (coccidae and diaspididae), lace bugs (tinoidae), stink bugs (pentatomidae), cinch bugs and other seed bugs (lvgaeidae), cicadas (cicadidae), spittlebugs (cercopids), squash bugs (coreidae), red bugs and cotton stainers (pyrrhocoridae): adults and larvae of the order acari (mites) including European red mite, two spotted spider mite, rust mites, McDaniel mite, and foliar feeding mites; adults and immatures of the order Orthoptera including grasshoppers; adults and immatures of the order Diptera including leafminers, midges, fruit flies

(tephritidae), and soil maggots; adults and immatures of the order

Thysanoptera including onion thrips and other foliar feeding thrips.

The compounds are also active against

economically important livestock, household, public and animal health pests such as: insect pests of the order Hymenoptera including carpenter ants, bees, hornets, and wasps; insect pests of the order Diptera including house flies, stable flies, face flies, horn flies, blow flies, and other muscoid fly pests, horse flies, deer flies and other

Brachycera, mosquitoes, black flies, biting midges, sand flies, sciarids, and other

Nematocera; insect pests of the order Orthoptera

including cockroaches and crickets; insect pests of the order Isootera including the Eastern subterranean termite and other termites; insect pests of the order Mallophaga and

Anoplura including the head louse, body louse, chicken head louse and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera

including the cat flea, dog flea and other fleas. The specific species for which control is exemplified are: fall armyworm, Spodoptera

fruigiperda; tobacco budworm, Heliothis virescens: boll weevil, Anthonomus grandis; aster leafhopper, Macrosteles fascifrons: black bean aphid, (Aphis

Fabae); southern corn rootworm, Diabrotica

undecimpunctata. The pest control protection afforded by the compounds of the present invention is not limited, however, to these species. The compounds of this invention may also be utilized as rodenticides.

Application

Arthropod pests are controlled and protection of agronomic crops, animal and human health is achieved by applying one or more of the Formula I 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. Because of the diversity of habitat and behavior of these arthropod pest species, many

different methods of application are employed. A preferred method of application is by spraying with equipment that distributes the compound in the

environment of the pests, on the foliage, animal, person, or premise, in the soil or animal, to the plant part that is infested or needs to be protected. Alternatively, granular formulations of these toxicant compounds can be applied to or incorporated into the soil. Other methods of application can also be employed including direct and residual sprays, aerial sprays, baits, eartags, boluses, foggers, aerosols, 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 which entice them to ingest or otherwise contact the compounds.

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, and synergists such as piperonyl butoxide often enhance the efficacy of the compounds of Formula I.

The rate of application of the Formula I compounds 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, etc. In general, application rates of 0.01 to 2 kg of active ingredient per hectare are sufficient to provide large-scale effective control of pests in agronomic ecosystems under normal

circumstances, but as little as 0.001 kg/hectare or as much as 8 kg hectare may be required. For

nonagronomic applications, effective use rates will range from about 1 to 50 mg/square meter but as little as about 0.1 mg/square meter or as much as 150

mg/square meter may be required.

The following Examples demonstrate the control efficacy of compounds of Formula I on specific pests; see Index Tables A and B for compound descriptions. Compounds not included in the Examples were either not screened or produced mortalities of less than 80%.

INDEX TABLE A

Example X R₃ R₂ R₁ Physical State

7 3-CF₃ H 4-F H oil

8 3-CF₃ H 4-F 2-F oil

9 3-CF₃ H 4-OEt H oil

10 3-CF₃ H 4-OCHF₂ H oil

11 3-CF₃ H 4-CH₃ H solid; mp: 84-86°C

12 3-CF₃ H 4-Br H very viscous oil

13 3-CF₃ H 4-OCH₃ H viscous oil

14 3-CF₃ H 3,4-OCH₂O- viscous oil

15 3-CF₃ H 4-OCH₂CF₃ H viscous oil

16 3-CF₃ H 4-Cl 3-Cl solid; mp: 96-99°C

17 3-CF₃ H 4-OCH₂C=CH H solid; mp: 76-78°C

Example X R₃ R₂ R₁ Physical State

18 2-Cl H 4-Cl H viscous oil

19 2-Cl H 4-F 2-F solid; mp: 79-81°C

20 2-Cl H 4-OCH₂C=CH H viscous oil

21 2-Cl H 4-OEt H viscous oil

22 2-Cl H 4-OCHF₂ H viscous oil

23 2-Cl H 4-OCH₂CF₃ H viscous oil

24 2-Cl H 4-CH₃ H viscous oil

25 2-Cl H 4-SCH₃ H viscous oil

INDEX TABLE B

Example R_x R₄ R₃ R₂ R₁ Physical State

H 3-Br 5-Br 4-F H oil

H 3-Br 5-Br 4-Cl H solid; mp: 113-115°C

H 3-Cl 5-Cl 4-tBu H oil

H 3-Cl 5-Cl 4-OCH₃ H oil

H 3-Cl 5-Cl 4-CHO H mp: 152-155°C

E 3-Cl 5-Cl 3-F H oil

H 3-Cl 5-Cl 3-Cl H solid; mp: 89-91°C

H 3-Cl 5-Cl 3-CH3 4-Cl solid; mp: 96.5-99°C

H 3-Cl 5-Cl 4-(4-CH₃C₆H₄ )CH₂O viscous semi-solid

H 3-Cl 5-Cl 4-(C(OCH₃ ) ₂CH₃ ) solid; mp: 133-135°C

E 3-Cl 5-Cl 4-C(O)CH₃ solid; mp: 137-140°C

H 3-Cl 5-Cl 4-SCH₃ oil

H 3-Cl 5-Cl 4-S (O) CH₃ pasty semi-solid

H 3-Cl 5-Cl 4-S ( O) ₂CH₃ oil

H 3-Cl 5-CF₃ 4-OCH₂C≡CH oil

Example R₄ R₃ R₂ R₁ Physical State

41 5-Cl H H OEt viscous oil

42 5-Cl H H Cl m.p. 138-141°C

43 5-Cl H H CF₃ very viscous oil

44 5-Cl 3-Cl H F viscous oil

45 6-Me 4-Me H CF₃ m.p. 97-100°C

46 4-Me H H CF₃ m.p. 118-120°C

47 5-Br H H F m.p. 128-129°C

48 5-Me H H F m.p. 123-125°C

49 5-OMe H H F viscous oil

50 6-Me 4-Me H F viscous oil

51 6-Me 4-Me H OEt waxy solid

52 5-Cl H H OCHF₂ viscous oil

53 5-Me H H OCHF₂ viscous oil

54 5-Cl 3-Cl H OCHF₂ viscous oil

55 6-Me 4-Me H OCH₂CF₃ viscous oil

56 5-CF₃ H H OCH₂CF₃ viscous oil

57 5-CF₃ H H Cl m.p. 133-135°C

58 5-Cl 3-Cl H OCH₂CF₃ very viscous oil

59 5-Cl 3-Cl H Br m.p. 105-107°C

60 5-Cl 3-Cl H CF₃ m.p. 87-89°C

61 5-Cl 3-Cl H Me m.p. 75-77°C

62 5-Cl 3-Cl 3-Cl Cl solid

63 5-CF₃ 3-Cl H Cl solid EXAMPLE J

Fall Armvworm

Test units, each consisting of an 8-ounce (230 mL) plastic cup containing a layer of wheat germ diet, approximately 0.5 cm thick, were prepared.

Five third-instar larvae of fall armyworm (Spodoptera frugiperda) were placed into each cup. Solutions of each of the test compounds (acetone/distilled water 75/25 solvent) were sprayed into the cups. Spraying was accomplished by passing the cups, on a conveyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at 30 p.s.i. (207 kPa). The cups were then covered and held at 27°C and 50% relative humidity for 72 hours, after which time readings were taken. Of the

compounds tested, the following gave mortality levels of 80% or higher: 1, 2* , 3*, 6, 7, 8, 14, 15, 16, 18, 20, 21, 23, 26, 27, 29, 31, 32, 33, 37, 40, 41, 43, 44 , 45, 47, 48, 51, 52, 53, 54, 56, 57 and 58.

*Tested at 0.137 kg/ha.

EXAMPLE K

Tobacco Budworm

The test procedure of Example J was repeated for efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that mortality was assessed at 48 hours. Of the compounds tested, the following gave mortality levels of 80% or

higher: 1, 3*, 7, 8, 14, 15, 16, 23, 25, 27, 28, 33, 42, 44 , 47, 50, 54 and 57.

*Tested at 0. 137 kg/ha EXAMPLE L

Southern Corn Rootworm

The units, each consisting of an 8-ounce (230 mL) plastic cup containing 1 sprouted corn seed, were prepared. The test units were sprayed as described in Example J with individual solutions of the test compounds. After the spray on the cups had dried, five third-instar larvae of the southern corn

rootworm (Diabrotica undecimounctata howardi) were placed into each cup. A moistened dental wick was inserted into each cup to prevent drying and the cups were then covered. The cups were then 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: 1, 2*, 7, 8, 9, 10, 11, 12, 13, 14, 15, 29, 37, 41, 45, 46, 47, 48, 50, 51, 53 and 56.

*Tested at 0.137 kg/ha.

EXAMPLE M

Aster Leafhopper

Test units were prepared from a series of

12-ounce (350 mL) cups, each containing oat (Avena sativa) seedlings in a 1-inch (2.54 cm) layer of sterilized soil. The test units were sprayed as described in Example J with individual solutions of the below-listed compounds. After the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the covered cups. The cups 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: 1, 2*, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 23, 24 , 29, 41, 43, 44, 45, 48, 54 and 57.

*Tested at 0.137 kg/ha.

EXAMPLE N

Boll Weevil

Five adult boll weevils (Anthonomus grandis grandis) were placed into each of a series of 9 ounce (260 mL) cups. The test procedure employed was then otherwise the same as in Example J. Mortality readings were taken 48 hours after treatment. Of the compounds tested, the following gave mortality levels of 80% or higher: 12, 13*, 16, 18, 43, 47 and 57.

*Tested at 0.137 kg/ha.

EXAMPLE O

Black Bean Aphid

Individual nasturtium leaves were infested with 5 to 10 aphids (all stages of Aphis fabae) and sprayed with their undersides facing up on a hydraulic sprayer as described in Example J. The leaves were then set in 1-inch diameter vials containing sugar water solution and covered with a clear plastic 1 oz - portion cup to prevent escape of aphids that drop from the leaves. 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: 1, 6, 7, 8, 10, 12, 13, 14, 15, 18, 20, 24, 40, 41, 44, 45 and 55. EXAMPLE P

Two-Spotted Spider Mite

One inch squares of kidney bean leaves that have been infested on the undersides with 25 to 30 adult mites (Tetranychus urtical) were sprayed with their undersides facing up on a hydraulic sprayer as described in Test A. The leaf squares were 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 cannot escape onto 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: 1, 7, 9, 10, 15, 18, 22, 30, 43, 44 , 47, 50, 56 and 57.

Claims

What is claimed is: 1. A compound having the formula

wherein

Q is selected from

R₁ is selected from the group halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₃-C₄ alkenyloxy, C₃-C₄ alkynyloxy, C₁-C₄

haloalkoxy, C₁-C₄ alkylthio, C₁-C₄

haloalkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ haloalkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, NO₂ and CN;

R₂ is selected from the group H, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄ alkenyloxy, C₂-C₄

alkynyloxy, C₂-C₄ alkenyl, C₂-C₄

haloalkenyl, C₂-C₄ alkynyl, C₂-C₄

alkoxycarbonyl, C₁-C₄ alkylamino, di-C₁-C₄ alkylamino, NO₂ and CN;

R₃ and X are independently selected from the group H, halogen, C₁-C₄ alkyl, C₁-C₄

haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄ alkoxycarbonyl, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ haloalkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, NO₂ and CN;

R₄ is selected from the group H, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy and CN;

w is selected from the group halogen, CF₃, OCF₃, C₁-C₄ alkyl, nitro, and C₁-C₄

alkoxycarbonyl; R_x is selected from the group H and halogen; R₆ is selected from the group C₁-C₄ alkyl; and R₇ is selected from the group C₁-C₄ alkyl.

2. A compound according to Claim 1 wherein R₁ is in the para position and R is H.

3. A compound according to Claim 2 wherein Q is Q-1.

4. A compound according to Claim 2 wherein Q is Q-2.

5. A compound according to Claim 4 wherein R₁ is selected from the group F, Cl, Br, CF₃,

OCH₂C=CH, OCHF₂ and OCF₃.

6. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound according to any one of Claims 1 to 5 and a carrier therefor.

7. A method for controlling arthropods comprising applying to them or to their environment an arthropodicidally effective amount of a compound according to any one of Claims 1 to 5.