TITLE ARTHROPODICIDAL IMIDAZOLIDINES

The arthropodicidal imidazolidines and related derivatives of this invention are characterized by a nitrogen containing heterocycle. This heterocycle distinguishes the compounds of this invention from the semicarbazones of WO 90/07495, WO 92/06076 and EP-A-462,456.

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:

A is H;

E is selected from the group H and ^-0 ₃ alkyl; or

A and E can be taken together to form a member selected from the group (CH ₂ ) _t , 0, S(0) _q , 0-CH ₂ , S(0)„CH ₂ and NR ⁵ ; each (CH ₂ ) can be optionally substituted with 1 or 2 substituents independently selected from the group 1 or 2 halogen atoms, C- _L -Cg alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halo- cycloalkyl, C -C ₇ alkylcycloalkyl, C ₂ -C ₄ alkoxy-

carbonyl and phenyl optionally substituted with 1, 2 or 3 groups independently selected from W; and when A and E are taken together to form OCH ₂ or S(0) _q CH ₂ , the CH ₂ moiety can be attached to the phenyl ring or to the carbon bearing E;

G is selected from the group C(0)C(0 , C(0)N(R ⁶ ) C(0) , C(0)C(R ⁷ )R ⁸ C(0) , C(R ⁷ )R ⁸ C(R ⁹ )R ¹⁰ and C(0)C(R ⁷ )R ⁸ ; when G is C(R ⁷ )R ⁸ C(R ⁹ )R ¹⁰ or C(0)C(R ⁷ )R ⁸ either carbon atom bearing the groups selected from R ⁷ -R ¹⁰ can be attached to either nitrogen atom of

-the urea moiety; R ¹ and R ² are independently selected from the group R ¹² , halogen, ^' CN, N0 ₂ , N ₃ , SCN, OR ¹² , SR ¹² , S(0)R ¹² , S(0) ₂ R ¹² , NR ¹² R ¹³ , C(0)R ¹² , C0 ₂ R ¹² , C(0)NR ¹² R ¹³ , OC(0)R ¹² , OC0 ₂ R ¹² OC(0)NR ¹² R ¹³ _Λ

NR^CCOJR ¹² , NR ¹³ C(0)NR ¹² R ¹³ , OS0 ₂ R ¹² and NR ¹³ S0 ₂ R ¹² ; when n is at least 2, R ¹ can be attached to adjacent carbon atoms to form a 5— or 6-membered fused ring as OCH ₂ 0, OCH ₂ CH ₂ 0 or CH ₂ CH ₂ 0 each CH ₂ optionally substituted with 1 or

2 substituents independently selected from the group halogen and methyl; when m is at least 2, R ² can be attached to adjacent carbon atoms to form a 5- or 6-membered fused ring as OCH 0, OCH ₂ CH ₂ 0 or CH ₂ CH ₂ 0, each CH ₂ optionally substituted with 1 or 2 substituents independently selected from the group halogen and methyl; R ³ is selected from the group H, C^Cg alkyl, C _j^ -C haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl,

C ₄ -C ₇ alk lcycloalkyl, C -C ₇ cycloalk lalkyl, C -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C -C ₆ haloalkynyl, C -Cg alkoxyalkyl, C -C ₆ cyanoalkyl, C ₃ -C ₈ alkox carbonylalkyl, OR ¹² , SCOgR ¹² , N(R ¹² )R ¹³ , CN, C0 ₂ R ¹² , C(0)R ¹² ,

C(0)N(R ¹² )R ¹³ , C(S)N(R ¹² )R ¹³ , C(S)R ¹² , phenyl optionally substituted with (R ¹⁴ ) _p and benzyl optionally substituted with 1, 2 or 3 groups independently selected from W; R ⁴ is selected from the group H, C-^-Cg alkyl, C^C haloalkyl, C -C ₆ alkenyl, C ₂ -C ₆ halolalkenyl, C ₂ -Cg alkynyl, C ₂ -C ₆ haloalkynyl, C ₂ -C ₆ alkoxyalkyl, C ₂ -Cg cyanoalkyl, phenyl optionally substituted with (R ¹ ) _p and benzyl optionally substituted with 1, 2 or 3 groups independently selected from W; R ⁵ is selected from the group H, C _x -C alkyl, C(0)R ¹² , C0 ₂ R ¹² , C(0)N(R ¹² )R ¹³ , C(S)N(R ¹² )R ¹³ , C(S)R ¹² , C(S)OR ¹² , SR ¹² , S(0)R ¹² , S0 ₂ R ¹² , P (O) (OR ¹¹ ) (OR ¹² ) , P(S) (OR ¹¹ ) (OR ¹² ) , P(O) (R ¹¹ ) (OR ¹² ), P (O) (R ¹¹ )SR ¹² , and phenyl optionally substituted with at least one group independently selected from W; R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are independently selected from the group H and C ₂ -C ₃ alkyl; R ¹¹ is selected from the group H, C ₁ -C ₆ alkyl, ^-C haloalkyl, C ₄ -C ₇ cycloalkylalkyl, C ₄ -C ₇ halocycloalkylalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -Cg alkynyl, C ₂ -Cg haloalkynyl, C ₂ -C ₆ alkoxyalkyl, C ₂ -C ₆ alkylthioalkyl, C ₁ -C ₆ nitroalkyl, C ₂ -C ₆ cyanoalkyl, C ₃ -C ₈ alkoxycarbonylalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, phenyl optionally substituted with at least one group independently selected from W, benzyl optionally substituted with 1, 2 or 3 groups independently selected from W;

R ¹² is selected from the group H, C ₁ -C ₆ alkyl, ^-Cg haloalkyl, C -C ₇ cycloalkylalkyl, C ₄ -C ₇ halocycloalkylalkyl, C ₂ -Cg alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -Cg alkynyl, C ₂ -C ₆ haloalkynyl, ^c ₂ ^-c ₆ alkoxyalkyl, C ₂ -C ₆ alkylthioalkyl, C^Cg

nitroalkyl, C ₂ -Cg cyanoalkyl, C ₃ -C ₈ alkoxycarbonylalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, phenyl optionally substituted with at least one group independently selected from W, and benzyl optionally substituted with 1,

2 or 3 groups independently selected from W;

R ¹³ is selected from the group H, C -C ₄ alkyl C ₂ -C alkenyl and C ₂ -C ₄ alkynyl; or R ¹² and R ¹³ are optionally taken together as (CH ₂ ) ₄ , (CH ₂ ) ₅ or (CH ₂ CH ₂ 0CH ₂ CH ₂ ) ;

R ¹⁴ is selected from the group R ¹² , halogen, CN, N0 ₂ , N ₃ , SCN, OR ¹² , SR ¹² , S(0)R ¹² _r S0 ₂ R ¹² , N(R ¹² )R ¹³ , C(0)R ¹² , C0 ₂ R ¹² , C(0)N(R ¹² )R ¹³ , S0 ₂ N(R ¹² )R ¹³ , 0C(0)R ¹² , 0C0 ₂ R ¹² , 0C(0)N(R ¹² )R ¹³ , N(R ¹³ ) C(0)R ¹² , N(R ¹³ )C(0)N(R ¹² )R ¹³ , 0S0 ₂ R ¹² and N(R ¹³ ) S0 ₂ R ¹² ; when p is at least 2, R ¹⁴ can be attached to adjacent carbon atoms to form a 5— or 6—membered fused ring as 0CH ₂ 0, 0CH ₂ CH ₂ 0 or CH ₂ CH ₂ 0, each CH ₂ optionally substituted with 1 or 2 substituents independently selected from the group halogen and methyl;

W is selected from the group halogen, CN, N0 ₂ , C ₁ -C ₂ alkyl, C _x -C ₂ haloalkyl, C ₁ -C ₂ alkoxy, C _x -C ₂ haloalkoxy, C ₁ -C alkylthio and C _x -C ₂ haloalkylthio, C ₁ -C ₂ alkylsulfonyl and C ₁ -C ₂ haloalkylsulfonyl;

X is selected from the group 0 and S; i is 1 to 4; n is 1 to 5; p is 1 to 3; q is 0 to 2; and t is 1 to 3.

Preferred Compounds A are compounds of Formula I wherein:

A and E are taken together to form a member of the group CH ₂ , CH ₂ CH ₂ and 0; R ¹ and R ² are independently selected from the group R ¹² , halogen, OR ¹² , SR ¹² , S(0)R ¹² and S0 ₂ R ¹² ; R ³ is selected from the group C ₁ -C ₆ alkyl and phenyl optionally substituted with (R ¹⁴ )_; R ⁴ is H;

R ¹² is selected from the group C; _| _-C ₃ alkyl and

C ₁ -C ₃ haloalkyl; R ¹⁴ is selected from the group R ¹² , halogen, CN, N0 ₂ , OR ¹² , SR ¹² , S(0)R ¹² , S0 ₂ R ¹² , C0 ₂ R ¹² and 0S0 ₂ R ¹² ; and m, n and p are independently 1 or 2.

In the above recitations, the term "alkyl" used either alone or in compound words such as "alkylthio" or "haloalkyl", denotes straight or branched alkyl such as methyl, ethyl, n-propyl, isopropyl and the different butyl, pentyl and hexyl isomers.

Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. Alkenyl denotes straight or branched chain alkenes such as vinyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers.

Alkynyl denotes straight chain or branched alkynes such as ethynyl, 1-proρynyl, 3-propynyl and the different butynyl, pentyjiyl and hexynyl isomers. Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term "halogen", either alone or in compound word 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 independently selected halogen atoms. Examples of haloalkyl include CH ₂ CH ₂ F, CF ₂ CF ₃ and CH ₂ CHFC1. The terms "haloalkenyl" and "haloalkynyl" are defined analogously to the term "haloalkyl".

The total number of carbon atoms in a substituent group is indicated by the "C^-C _j " prefix where i and j are numbers from 1 to 8. For example, C ₄ alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including 0CH ₂ 0CH ₂ CH CH ₃ and 0CH ₂ CH ₂ 0CH ₂ CH ₃ .

When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents.

Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active than the others and how to separate said stereoisomers. Accordingly, the present invention comprises ^{^} racemic mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.

DETAILS OF THE INVENTION Compounds of Formula I are prepared according to Schemes 1 through 5 with substituents as previously defined, unless otherwise noted.

II

Compounds of Formula I (G=C (0) C (0) ) are prepared by reaction of compounds of Formula II with electrophiles of Formula III and expulsion of two molar equivalents of HZ. The reaction takes place in conventional organic solvents such as dichloromethane, 1,2-dichloroethane, chloroform, ether, tetrahydrofuran and hexanes. The reaction can be conducted at temperatures between -20°C and 100°C with the boiling temperature of the solvent being generally preferred.

Compounds of Formula II are disclosed in WO 90/07495, WO 92/06076 and EP-A-462, 456. Compounds of Formula III are well known to those skilled in the art as oxalylhalides that are highly reactive electrophiles .

Scheme 2

R ⁶ =H

Compounds of Formula I (G=C (O) (R ⁶ ) C (0) ; R ⁶ =H) are formed by reaction of compounds of Formula II with chlorocarbonyl isocyanate (Angew. Chem . Int . Ed. Engl . , 1977, 16, 743) . The reaction takes place in conventional organic solvents such as dichloromethane, 1, 2-dichloro- ethane, chloroform, ether, tetrahydrofuran and hexanes. The reaction can be conducted at temperatures between

-20°C and 100°C with the boiling temperature of the solvent being generally preferred.

Scheme 3

II ^► I (G=C(0)C(R ⁷ ) (R ⁸ )C(0))

v

Z= alogen, alkoxy

Compounds of Formula I (G=C(0)C(R ⁷ ) (R ⁸ )C(0)) are formed by reaction of compounds of Formula II with compounds of Formula V. The reaction takes place in the presence of a base such as an alkali metal, tertiary amine, metal hydride and the like in conventional organic solvents such as dichloromethane, 1,2-dichloroethane, chloroform, ether, tetrahydrofuran and hexanes. The reaction can be conducted at temperatures between -20°C and 100°C with the boiling temperature of the solvent being generally preferred (Znd. Chemist, 1945, 21, 678) . Formula V compounds are well known to those skilled in the art as alonates that are obtained by known literature methods.

Scheme 4

Base

II ► I (G=C(R) 7',(τR_8 ^ϋ _λ )C,( _T R ₅ 9-',) ,( ₀ R1- ¹ -0",))

R ⁸ R ⁹ 7 \ / _R in Z=C1,Br,1,0S0 ₂ R (R=alkyl,phenyl)

VI

Compounds of Formula I (G=C (R ⁷ ) (R ⁸ ) C (R ⁹ )R ¹⁰ ) ) are formed by reaction of compounds of Formula II with vicinal dihalides or disulfonates of Formula VI. The reaction takes place in the presence of a base such as an alkali metal, tertiary amine, metal hydride and the like in conventional organic solvents including ether, tetrahydrofuran, 1, 2-dimethoxyethane, methylene chloride, chloroform, N,N-dimethylformamide and dimethylsulfoxide. The reaction can be conducted at temperatures in the range of -100°C to 100°C. Several compounds of

Formula VI are well known to those skilled in the art as ethylenedihalides and are known to react in the above fashion.

Scheme 5

II (G=C(0)C(R ⁷ ) (R ⁸ ) )

VII

Compounds of Formula I (G= (C(O) C(R ⁷ ) (R ⁸ ) ) are formed by reaction of compounds of Formula II with α-halo carbonylhalides of Formula VII. The reaction takes place in the presence of a base such as a tertiary amine, metal hydride and the like in conventional organic solvents including ether, tetrahydrofuran, 1,2-dimethoxyethane, methylene chloride and chloroform. The reaction can be conducted at temperatures in the range of -100°C to 100°C. Compounds of Formula VII are well known to those skilled in the art.

It is recognized that in many of the transformations described, it is necessary to utilize appropriate protecting groups to prevent unwanted side reactions or

use reagents that do not affect functional groups other than those desired to be changed. One skilled in the art will be able to select appropriate protecting groups and reagents to this end. EXAMPLE 1

1-r r5-Fluoro-2- (4-fluorophenyl) -2 _r 3-dihydro-lH-inden-l- ylidenelaminoT-3-T4- (tri luoromethyl)phen ll - i-midazolidinetrione To a solution of 2-[5-Fluoro-2-(4-fluorophenyl) -2,3- dihydro-lH-inden-1-ylidene] -N-[4- (trifluoromethyl) - phenyl]hydrazinecarboxamide (1.0 g, 0.0022 mol) in methylene chloride (20 L) was added oxalyl chloride (0.37 g, 0.003 mol) . The resulting solution was refluxed 18 hours, cooled to room temperature and concentrated under reduced pressure. The resulting oil was triturated with ether and 1.0 g of the title compound was isolated as a white crystalline solid, mp 200-201°C ^X H NMR (CDC1 ₃ ) 5 8.0 (dd, IH) , 7.5 (ABq, 4H) , 7.1 ( , 6H) , 4.4 (dd, IH) , 3.4 (AB of ABX, 2H) . EXAMPLE 2

1-rr5-Fluoro-2- (4-fluorophenyl) -2 _f 3-dihydro-lH-inden-l- ylidenel aminol-3-F4- (trifluoromethyl)phenyll -1 _r 3-5- triazine-2 _f 4 _r (IH, 3H, 5H) -trione To a solution of 2-[5-Fluoro-2- (4-fluorophenyl)-2,3- dihydro-lH-inden-1-ylidene]-N-[4-(trifluoromethyl)- phenyl]hydrazinecarboxamide (1.0 g, 0.0022 mol) in methylene chloride (20 L) was added N-(chlorocarbonyl) - isocyanate (0.35 g, 0.0034 mol) . The reaction was heated to reflux for 18 hours, cooled to room temperature and concentrated under reduced pressure. The resulting solid was washed with ether and the title compound isolated as a yellow crystalline solid, mp 251°C ^X R NMR (DMSO) 10.4 (s, IH) , 8.0 (m, 2H) , 7.7 (s, 4H) , 7.5-7.1 (m, 5H) , 4.1 (m, 3H) .

By the procedures described herein the following compounds of Tables 1 to 8 can be prepared. The compounds in Table 1, line 1 can be referred to as 1-1, 1-2, 1-3, 1-4 and 1-5 (as designated by line and column) . All the other specific compounds covered in these Tables can be designated in an analogous fashion. The following abbreviations have been used in Tables 1-8: Me = methyl Et = ethyl

Pr = n-propyl iPr = isopropyl Ph = phenyl

Key for Tables

Q=

Q-l Q-2

Q-3 Q-4

Q-5 Q-6

Q-7 Q-8

Table 1

Q=Q-l L=CH ₂ ; R ¹ =CF ₃ ; R ³ =CH ₃ ; R ² = =CH ₂ ; R ¹ =OCF ₃ ; R ³ =CH ₃ ; R ² = L=CH ₂ ; R^Br; R ³ =CH ₃ ; R ² = =CH ₂ ; R ¹ =CF ₃ ; R ³ =Et; R ² = =CH ₂ ; R ¹ =OCF ₃ ; R ³ =Et; R ² = =CH ₂ ; R ¹ =Br; R ³ =Et; R ² = =CH ₂ ; R ¹ =CF ₃ ; R ³ =nPr; R ² = L=CH ₂ ; R ¹ =OCF ₃ ; R ³ =nPr,- R ² = =CH ₂ ; R ¹ =Br; R ³ =nPr; R ² = =CH ₂ ; R ¹ =CF ₃ ; R ³ =iPr; R ² = =CH ₂ ; R ¹ =OCF ₃ ; R ³ =iPr; R ² = L=CH ₂ ; R^Br; R ³ =iPr; R ² = L=CH ₂ ; R ¹ =CF ₃ ; R ³ =Ph; R ² = =CH ₂ ; R ¹ =OCF ₃ ; R ³ =Ph.; R ² = =CH ₂ ; R ¹ =Br; R ³ =Ph; R ² = L=CH ₂ ; R ¹ =CF ₃ ; R ³ =4-F-Ph; R ² = L=CH ₂ ; R ¹ =OCF ₃ ; R ³ =4-F-Ph; R ² = =CH ₂ ; R ¹ =Br; R ³ =4-F-Ph; R ² = =CH ₂ ; R ¹ =CF ₃ ; R ³ =4-Cl-Ph; R ² = L=CH ₂ ; R ¹ =OCF ₃ ; R ³ =4-Cl-Plι; R ² = L=CH ₂ ; R ¹ =Br; R ³ =4-Cl-Ph; R ² = =0; R ¹ =CF ₃ ; R ³ =Me; R ² = L=0; R ¹ =OCF ₃ ; R ³ =Me; R ² = L=0; R ^x =Br; R ³ =Me,- R ² =

L=0; R >1- ==,CF ₃ ; R 3°_=τEt; R _? 2- ₌ L=0; R ¹ =OCF ₃ ; R ³ =Et; R ² = L=0; R^Br R ³ =Eb; R ² = L=0; R ¹ =CF ₃ ; R ³ =Pr; R ² = L=0 R ¹ =OCF ₃ ; R ³ =Pr,- R ² = =0; R^Br; R ³ =Pr; R ² = =0; R ¹ =CF ₃ ; R ³ =iPr; R ² = L=0; R ¹ =OCF ₃ ; R ³ =iPr; R ² =

Table 2

Q=Q-2 R ¹ =CF ₃ ; R ³ =CH ₃ ; R ² = R ¹ =OCF ₃ ; R ³ =CH ₃ ; R ² = R ¹ =Br; R ³ =CH ₃ ; R ² = R ¹ =CF ₃ ; R ³ =Et; R ² = R ¹ =OCF ₃ ; R ³ =Et; R ² = R ¹ =Br; R ³ =Et; R ² = R1=CF ₃ ; R ³ =nPr; R ² = R ¹ =OCF ₃ ; R ³ =nPr; R ² = R^Br; R ³ =nPr; R ² =

R »1 ⁱ ==,CF ₃ ; R 3 ^J ₌ =i ₁ - Pr; R >2 ₌ = R ¹ =OCF ₃ ; R ³ =iPr; R ² = R^Br; R ³ =iPr; R ² = R ¹ =OCF ₃ ; R ³ =Ph; R ² = R ^X =Br; R ³ =Ph; R ² = R ¹ =CF ₃ ; R ³ =4-F-Ph; R ² = R ¹ =OCF ₃ ; R ³ =4-F-Ph; R ² = R1=BΓ; R ³ =4-F-Ph; R ² = R ¹ =CF ₃ ; R ³ =4-Cl-Ph; R ² = R ¹ =OCF ₃ ; R ³ =4-Cl-Ph; R ² = R ¹ =Br; R ³ =4-Cl-Ph; R = i CF ₃ ; R >3 ^J ₌ =, e; R 2^_= ¹ =OCF ₃ ; R ³ = e; R ² = ¹ =Br; R ³ =Me; R ² = !=CF ₃ ; R ³ =Et; R ² = ¹ =OCF ₃ ; R ³ =Et; R ² = ^Br; R ³ =Et; R ² = ¹ =CF ₃ ; R ³ =Pr; R ² = ¹ =OCF ₃ ; R ³ =Pr; R ² = ¹⁼ Br; R ³ =Pr; R = ^ =CF ₃ ; R ³ =iPr; R ² = ¹ =OCF ₃ ; R ³ =iPr; R ² =

Table 3

Q=Q-3 L=CH ₂ ; R ¹ =CF ₃ ; R ³ =CH ₃ ; R ² = =CH ₂ ,- R ¹ =OCF ₃ ; R ³ =CH ₃ ; R ² = =CH ₂ ; R ^X =Br; R ³ =CH ₃ ; R ² = =CH ₂ ; R ¹ =CF ₃ ; R ³ =Et; R ² = L=CH ₂ ; R ¹ =OCF ₃ ; R ³ =Et; R ² = =CH ₂ ; R^Br,- R ³ =Et; R ² = =CH ₂ ; R ¹ =CF ₃ ; R ³ =nPr,- R ² = L=CH ₂ ; R ¹ =OCF ₃ ; R ³ =nPr; R ² = =CH ₂ ; ^Br R ³ =nPr; R ² = L=CH ₂ ; R ¹ =CF ₃ ; R ³ =iPr; R ² = =CH ₂ ; R ¹ =OCF ₃ ; R ³ =iPr; R ² = L=CH ₂ ; R ¹ =Br? R ³ =iPr; R ² = =CH ₂ ; R ¹ =CF ₃ ; R ³ =Ph; R ² = =CH ₂ ; R ¹ =OCF ₃ ; R ³ =Ph; R ² = L=CH ₂ ; R ^x =Br; R ³ =Ph; R ² = L=CH ₂ R ¹ =CF ₃ ; R ³ =4-F-Ph; R ² = =CH ₂ ; R ¹ =OCF ₃ ; R ³ =4-F-Piι; R ² = L=CH ₂ ; R ¹ =Br; R ³ =4-F-Ph; R ² = L=CH ₂ ; R ¹ =CF ₃ ; R ³ =4-Cl-Ph; R ² = L=CH ₂ ; R ¹ =OCF ₃ ; R ³ =4-Cl-Plι; R ² = =CH ₂ ; R ¹ =Br; R ³ =4-Cl-Ph,- R ² = L=0; R ¹ =CF ₃ ; R ³ =Me; R ² = L=0; R ¹ =OCF ₃ ; R ³ = e; R ² = L=0; R ^x =Br; R ³ =Me; R ² = =0; R ¹ =CF ₃ ; R ³ =Et; R ² = =0; R ¹ =OCF ₃ ; R ³ =Et; R ² = =0; R ^x =Br; R ³ =Et; R ² = L=0; R ¹ =CF ₃ ; R ³ =Pr; R ² = L=0; R ¹ =OCF ₃ ; R ³ =Pr; R ² = L=0; R ¹ =Br; R ³ =Pr; R ² = L=0; R ¹ =CF ₃ ; R ³ =iPr; R ² = =0; R ¹ =OCF ₃ ; R ³ =iPr,- R ² =

Table 5

Q=Q-5 I.=CH ₂ ; R ¹ =CF ₃ ,- R ³ =CH ₃ ; R ² = L=CH ₂ ; R ¹ =OCF ₃ ; R ³ =CH ₃ ; R ² = =CH ₂ ; R ¹ =Br; R ³ =C ; R ² = L=CH ₂ ,- R ¹ =CF ₃ ; _R ³ =Et; R ² = L=CH ₂ ; R ^x =OCF ₃ ; R ³ =Et R ² =

L=CH ₂ ; R ^x =Br; R ³ =Et; R _? 2 ² ₌ = =CH ₂ ; R ¹ =CF ₃ ; R ³ =nPr; R ² = L=CH ₂ ; R ¹ =OCF ₃ ; R ³ =nPr; R ² = L=CH ₂ ; R ¹ =Br; R ³ =nPr; R ² = =CH ₂ ; R ¹ =CF ₃ ; R ³ =iPr; R ² = L=CH ₂ ; R ¹ =OCF ₃ ; R ³ =iPr; R ² = =CH ₂ ; R^Br; R ³ =iPr; R ² = L=CH ₂ ; R ¹ =CF ₃ ; R ³ =Ph; R ² = L=CH ₂ ; R ¹ =OCF ₃ ; R ³ =Ph; R ² = =CH ₂ ; R ¹ =Br; R ³ =PH; R ² = =CH ₂ ; R ¹ =CF ₃ ; R ³ =4-F-Ph; R ² = L=CH ₂ ; R ¹ =OCF ₃ ; R ³ =4-F-Ph; R ² = L=CH ₂ ; R-^B ; R ³ =4-F-Ph; R ² = R ³ =4-Cl-Ph; R ² = I.=CH ₂ ; R ¹ =OCF ₃ ; R ³ =4-Cl-Ph; R ² = L=CH ₂ ; R ¹ =Br; R ³ =4-Cl-Ph.; R ² = L=0; R ¹ =CF ₃ ; R ³ =Me; R ² = -L=0; R ¹ =OCF ₃ ; R ³ =Me; R ² = L=0; R ¹ =Br; R ³ =Me; R ² = L=0; ]??-=CF ₃ ; R ³ =Et; R ² = L=0; R ¹ =OCF ₃ ; R ³ =Et; R ² = -L=0; R ^x =Br; R ³ =Et; R ² = -L=0; R ¹ =CF ₃ ; R ³ =Pr; R ² = L=0; R ¹ =0CF ₃ ; R ³ =Pr; R ² = L=0; R^Br R ³ =Pr; R ² = - =0; R ^X =CF ₃ ; R ³ =iPr; R ² = L=0; R ¹ =0CF ₃ ; R ³ =iPr; R ² =

Table 6

Table 7

0=0.-7 W=H; R ¹ =CF ₃ ; R ² = W=H; R ¹ =OCF ₃ ; R ² = W=H; R ¹ =Br; R ² = W=F; R ¹ =CF ₃ ; R ² = W=F; R ¹ =OCF ₃ ; R ² = W=F; R^B ; R ² = W=C1; R ¹ =CF ₃ ; R ² = =C1; R ¹ =OCF ₃ ; R ² = =C1; R^Br; R ² =

Table 8

Q=Q-8 W=H; R ¹ =CF ₃ ; R ² = W=H; R ¹ =OCF ₃ ; R ² = W=H; R ^x =Br; R ² = W=F; R ¹ =CF ₃ ; R ² = W=F; R ¹ =OCF ₃ ; R ² = W=F; R ^x =Br; R ² = W=C1; R ¹ =CF ₃ ; R ² = =C1; R ¹ =OCF ₃ R ² = W=C1; R^B ; R ² =

Formulatio /Utility

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. Use formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. 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 100 weight percent.

Wei ht Percent

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 and solvents 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, 196 A, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced be agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp. 251-259. 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 Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pages 147 and following, Perry 's Chemical Engineer 's

Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 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 also be prepared as taught in DE 3,246,493.

For further information regarding the art of formulation, see U.S. Patent 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41; U.S. Patent 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. Patent 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. , iVeed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all percentages are by weight and all formulations are worked up in conventional ways . Compound numbers refer to compounds in Index Table A.

Example A

Wettable Powder

Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

Example B Granule Compound 1 10.0% attapulgite granules (low volative matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.

Example C

Extruded Pellet

Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.

Example D Emulsifiable Concentrate Compound 1 20.0% blend of oil soluble sulfonates

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and polyoxyethylene ethers 10.0% isophorone 70.0%.

The compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term 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 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 Nemata. The compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Phthiraptera, Siphonoptera, Blattaria, Thysanaura and Pscoptera; pests belonging to the Class Arachnida and Phylum Platyhelminth.es. 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, semiochemicals, repellants, 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 other agricultural protectants with which compounds of this invention can be formulated

are: insecticides such as avermectin B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion- methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fonophos, isofenphos, methidathion, methamidophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole, difenoconazole, diniconazole, fluquinconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride, furalaxyl, folpet and flusilazol; nematocides such as aldoxycarb, fenamiphos and fosthietan; bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite and fenbutatin oxide; and biological agents such as Bacillus thuringiensis and baculovirus. In certain instances, combinations with other arthropodicides having a similiar spectrum of control but a different mode of action will be particularly advantageous for resistance management.

Arthropod pests are controlled and protection of agronomic crops, animal and human health is achieved by applying one or more of the compounds of this invention,

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26

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, systemic uptake, baits, eartags, boluses, foggers, fumigants, 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.

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, and synergists and other solvents 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, _v 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. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Table A for compound descriptions.

Index Table A

E ² E ^J £ mp ( °C ,

5-F 4-F-Ph C(0)C(0) 188-189

5-F 4-F-Ph C(0)C(0) 200-201

5-F Me C(0)C(0) 96-97

4-F Et C(0)C(0) 126-127 5-F 4-F-Ph C(0)NHC(0) 251

TEST A Fall Armyworm 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. Ten third- instar larvae of fall armyworm { Spodoptera frugiperda ) were placed into a cup. Solutions of each of the test compounds (acetone/distilled water 75/25 solvent) were sprayed into the cups, a single solution per set of three 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 resulted in greater than or equal to 80% mortality: 1, 2 and 4.

TEST B Tobacco Budworm

The test procedure of Test A 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 resulted in greater than or equal to 80% mortality: 1 and 2.

TEST C Southern Corn Rootworm

Test units, each consisting of an 8-ounce (230 mL) plastic cup containing 1 sprouted corn seed, were prepared. Sets of three test units were sprayed as described in Test A 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 undecimpunctata 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 resulted in greater than or equal to 80% mortality: 1, 2, 3 and 4.

TEST D Aster Leafhopper

Test units were prepared from a series of 12-ounce (350 mL) cups, each containing oat {Avena sat±va) seedlings in a 1-inch (2.54 cm) layer of sterilized soil. The test units were sprayed as described in Test A 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. None of the compounds tested resulted in greater than 80% mortality.

TEST E Boll Weevil

Five adult boll weevils (Anthonomus 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 Test A with three cups per treatment. Mortality readings were taken 48 hours after treatment. Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 1, 2, 3 and 4.