Insecticidal N-(heteroarylalkyl)alkanediamine derivatives

1. A compound of formula I

wherein

—Ar is selected from

where

R 1 , R 2 , R 3 , and R 4 are independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl, and haloalkoxy;

and,

s is an integer selected from 0 or 1;

-a and r are integers independently selected from 0 or 1;

—R is selected from hydroxy, haloalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkylalkyl, cyanoalkyl, formyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, dialkylphosphonato, oxolan-3-ylmethyl, 2H-3,4,5,6-tetrahydropyran-2-ylmethyl, cyclohex-1-en-3-yl, thien-3-ylmethyl, furan-2-ylmethyl, furan-3-ylmethyl, benzo[b]furan-2-ylmethyl, 2-R 8 -1,3-thiazol-4-ylmethyl, 5-R 8 -1,2,4-oxadiazol-3-ylmethyl,

where

R 8 is selected from halogen, alkyl, aryl, and heteroaryl, wherein aryl and heteroaryl are optionally substituted with at least one of halogen, alkyl, haloalkyl, alkoxy, and haloalkoxy;

m is an integer selected from 1 or 2;

and,

R 9 , R 10 , R 11 , R 12 , and R 13 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyiminoalkyl, cyano, nitro, 2-alkyl-2H-tetrazol-5-yl, aryl, and aryloxy;

R 14 , R 15 and R 16 are independently selected from hydrogen, halogen, alkyl and aryl;

R 17 is selected from hydrogen, alkyl,

where

R 18 , R 19 , R 20 , R 21 , and R 22 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, and haloalkoxy;

—R a , R b , R c and R d are independently selected from hydrogen and alkyl;

-b and c are integers independently selected from 0 or 1;

and

when b and c are 1,

—R e , R f , R g and R h are independently selected from hydrogen and alkyl;

—R 5 is selected from hydrogen, alkyl, and

where

n is an integer selected from 1 or 2; and,

R 23 , R 24 , R 25 , R 26 , and R 27 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, and haloalkoxy;

-d and e are integers independently selected from 0 and 1;

and,

when d and e are 1;

—U and V are —CH 2 —;

—R 6 is selected from hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxyalkyl, alkenyl, haloalkenyl, and

where

p is an integer selected from 1 and 2;

and,

R 28 , R 29 , R 30 , R 31 and R 32 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, and haloalkoxy;

—R 7 is selected from —C≡N and —NO 2 ;

—W is selected from —CR 33 — and —N—;

—X is elected from —CR 34 R 35 —, —O—, —S—, and —NR 36 ;

where

R 33 , R 34 , R 35 and R 36 are independently selected from hydrogen and alkyl;

provided that

I) when i) Ar is oxolan-3-yl (M); ii) a, b and c are 1, and R a through R g , inclusively, are hydrogen; iii) d, e and r are 0; iv) R is —(CH 2 ) m CR 14 ═CR 16 or —(CH 2 ) m C≡CR 17 ; v) R 5 is hydrogen or alkyl; vi) R 6 is hydrogen, alkyl, alkenyl or haloalkenyl and vii) W is —CR 33 — where R 33 is hydrogen; viii) then X is other than —S—;

II) when d and e are 0,

—R 5 and X may be taken together with —CH 2 (CH 2 ) q — or —CH 2 YCH 2 — to form a ring,

where

q is an integer selected from 1 or 2;

Y is selected from O, S and NR 37 , where R 37 is hydrogen or alkyl;

—X is elected from —CH—, —O—, —S—, and —N—;

and

III) when X is —CH— or —N—,

R 6 is selected from hydrogen, alkyl and that set forth above for R;

when b and c are 0,

—R and R 5 may be taken together with —CH 2 CH 2 — to form a piperazine ring;

or

agriculturally acceptable salt thereof.

2. A compound of claim 1 , wherein a is 1; b, c, d and e are each 0; R a , R b , R c and R d are each hydrogen; R 5 is selected from hydrogen and alkyl; W is selected from —CR 33 — and —N—, where R 33 is hydrogen; X is selected from —O—, —S—, and —NR 36 —;

and

R 5 and X may be taken together with —CH 2 (CH 2 ) q — or —CH 2 YCH 2 — to form a ring,

where

Y is selected from —O— and —NR 37 —, where R 37 is hydrogen or alkyl; X is —N— and R 6 is selected from hydrogen and alkyl.

3. A compound of claim 2 , wherein Ar is selected from

where

s is 0; R 1 , R 2 and R 4 are each hydrogen and R 3 is halogen.

4. A compound of formula I

wherein

—Ar is selected from

where

R 1 , R 2 , R 3 , and R 4 are independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl, and haloalkoxy;

and,

s is an integer selected from 0 or 1;

-a and r are integers independently selected from 0 or 1;

—R is selected from hydroxy, haloalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkylalkyl, cyanoalkyl, formyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, dialkylphosphonato, oxolan-3-ylmethyl, 2H-3,4,5,6-tetrahydropyran-2-ylmethyl, cyclohex-1-en-3-yl, thien-3-ylmethyl, furan-2-ylmethyl, furan-3-ylmethyl, benzo[b]furan-2-ylmethyl, 2-R 8 -1,3-thiazol-4-ylmethyl, 5-R 8 -1,2,4-oxadiazol-3-ylmethyl,

where

R 8 is selected from halogen, alkyl, aryl, and heteroaryl, wherein aryl and heteroaryl Are optionally substituted with at least one of halogen, alkyl, haloalkyl, alkoxy, and haloalkoxy;

m is an integer selected from 1 or 2;

and,

R 9 , R 10 , R 11 , R 12 , and R 13 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyiminoalkyl, cyano, nitro, 2-alkyl-2H-tetrazol-5-yl, aryl, and aryloxy;

R 14 , R 15 and R 16 are independently selected from hydrogen, halogen, alkyl and aryl;

R 17 is selected from hydrogen, alkyl,

where

R 18 , R 19 , R 20 , R 21 , and R 22 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, and haloalkoxy;

—R a , R b , R c and R d are independently selected from hydrogen and alkyl;

-b and c are integers independently selected from 0 or 1;

and

when b and c are 1,

—R e , R f , R g and R h are independently selected from hydrogen and alkyl;

—R 5 is selected from hydrogen, alkyl, and

where

n is an integer selected from 1 or 2; and,

R 23 , R 24 , R 25 , R 26 , and R 27 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, and haloalkoxy;

-d and e are integers independently selected from 0 and 1;

and,

when d and e are 1;

—U and V are —CH 2 —;

—R 6 is selected from hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxyalkyl, alkenyl, haloalkenyl, and

where

p is an integer selected from 1 and 2;

and,

R 28 , R 29 , R 30 , R 31 and R 32 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, and haloalkoxy;

—R 7 is selected from —C≡N and —NO 2 ;

—W is selected from —CR 33 — and —N—;

—X is elected from —CR 34 R 35 —, —O—, —S—, and —NR 36 —;

where

R 33 , R 34 , R 35 and R 36 are independently selected from hydrogen and alkyl;

provided that when

i) Ar is oxolan-3-yl (M); ii) a, b and c are 1, and R a through R g , inclusively, are hydrogen; iii) d, e and r are 0; iv) R is —(CH 2 ) m CR 14 ═CR 15 R 16 or —(CH 2 ) m C≡CR 17 ; v) R 5 is hydrogen or alkyl; vi) R 6 is hydrogen, alkyl, alkenyl or haloalkenyl and vii) W is —CR 33 — where R 33 is hydrogen; viii) then X is other than —S—;

or

an agriculturally acceptable salt thereof.

5. A compound of claim 4 , wherein a is 1; b, c, d and e are each 0; R a , R b , R c and R d are each hydrogen; R 5 is selected from hydrogen and alkyl; W is selected from —CR 33 — and —N—, where R 33 is hydrogen and X is selected from —O—, —S—, and —NR 36 —.

6. A compound of claim 5 , wherein Ar is selected from

where

is 0; R 1 , R 2 and R 4 are each hydrogen and R 3 is halogen.

7. A compound of formula I

wherein

—Ar is selected from

where

R 1 , R 2 , R 3 , and R 4 are independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl, and haloalkoxy;

and,

s is an integer selected from 0 or 1;

-a and r are integers independently selected from 0 or 1;

—R is selected from hydrogen, hydroxy, alkyl, haloalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkylalkyl, cyanoalkyl, formyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, dialkylphosphonato, oxolan-3-ylmethyl, 2H-3,4,5,6-tetrahydropyran-2-ylmethyl, cyclohex-1-en-3-yl, thien-3-ylmethyl, furan-2-ylmethyl, furan-3-ylmethyl, benzo[b]furan-2-ylmethyl, 2-R 8 -1,3-thiazol-4-ylmethyl, 5-R 8 -1,2,4-oxadiazol-3-ylmethyl,

where

R 8 is selected from halogen, alkyl, aryl, and heteroaryl, wherein aryl and heteroaryl are optionally substituted with at least one of halogen, alkyl, haloalkyl, alkoxy, and haloalkoxy;

m is an integer selected from 1 or 2;

and,

R 9 , R 10 , R 11 , R 12 , and R 13 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyiminoalkyl, cyano, nitro, 2-alkyl-2H-tetrazol-5-yl, aryl, and aryloxy;

R 14 , R 15 and R 16 are independently selected from hydrogen, halogen, alkyl and aryl;

R 17 is selected from hydrogen, alkyl,

where

R 18 , R 19 , R 20 , R 21 , and R 22 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, and haloalkoxy;

—R a , R b , R c and R d are independently selected from hydrogen and alkyl;

-b and c are integers independently selected from 0 or 1;

and

when b and c are 1,

—R e , R f , R g and R h are independently selected from hydrogen and alkyl;

-d and e are 0;

—R 5 and X are taken together with —CH 2 (CH 2 ) q — or —CH 2 YCH 2 — to form a ring,

where

q is an integer selected from 1 or 2;

Y is selected from —O—, —S— and —NR 37 —, where R 37 is hydrogen or alkyl;

—X is elected from —CH—, —O—, —S—, and —N—;

where

when X is —CH— or —N—,

—R 6 is selected from hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxyalkyl, alkenyl, haloalkenyl, and

where

p is an integer selected from 1 and 2;

and,

R 28 , R 29 , R 30 , R 31 and R 32 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, and haloalkoxy;

—R 7 is selected from —C≡N and —NO 2 ;

—W is selected from —CR 33 — and —N—, where R 33 is selected from hydrogen and alkyl;

or

an agriculturally acceptable salt thereof.

8. A compound of claim 7 , wherein a is 1; b, c, d and e are each 0; R a , R b , R c and R d are each hydrogen; W is selected from —CR 33 — and —N—, where R 33 is hydrogen; Y is selected from —O— and NR 37 ; X is —N— and R 6 is selected from hydrogen and alkyl.

9. A compound of claim 5 , wherein Ar is selected from

where

is 0; R 1 , R 2 and R 4 are each hydrogen and R 3 is halogen.

10. A composition comprising an insecticidally effective amount of a compound of claim 1 and at least one agriculturally acceptable extender or adjuvant.

11. The insecticidal composition of claim 10 , further comprising one or more second compounds selected from the group consisting of pesticides, plant growth regulators, fertilizers and soil conditioners.

12. A method of controlling insects, comprising applying an insecticidally effective amount of a composition of claim 10 to a locus where insects are present or are expected to be present.

13. A method of controlling insects, comprising applying an insecticidally effective amount of a composition of claim 11 to a locus where insects are present or are expected to be present.