IP Library Granted Patent US 8,618,126
Granted Patent B2
US 8,618,126 · App. 12/970,670 · Granted Dec 31, 2013

Antiparisitic dihydroazole compounds and compositions comprising same

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Quick Facts
Patent No.
US 8,618,126
App. No.
12/970,670
Granted
Dec 31, 2013
Kind
B2
Abstract

The present invention relates to novel dihydroazole of formula (I) and salts thereof: Wherein R 1 , A 1 , A 2 , G, X and Y are as defined in the description, compositions thereof, processes for their preparation and their uses to prevent or treat parasitic infections or infestations in animals and as pesticides.

Claims (397)

1. A dihydroazole compound of formula (I), or a pharmaceutically or agriculturally acceptable salt thereof:

wherein:

R 1 is halogen, —CN, or alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, halocycloalkyl, alkylcycloalkyl or cycloalkylalkyl, each which is unsubstituted or substituted with one or more of halogen, hydroxy, amino, alkyl- or di(alkyl)amino, alkyl, cycloalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, R 7 S(O)—, R 7 S(O) 2 —, R 7 C(O)—, R 7 R 8 NC(O)—, R 7 OC(O)—, R 7 C(O)O—, R 7 C(O)NR 8 —, —CN or —NO 2 ;

X is aryl or heteroaryl, which may be unsubstituted or substituted by one or more of halogen, hydroxy, amino, alkyl- or di(alkyl)amino, alkyl, cycloalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, R 7 S(O)—, R 7 S(O) 2 —, R 7 C(O)—, R 7 R 8 NC(O)—, R 7 OC(O)—, R 7 C(O)O—, R 7 C(O)NR 8 —, —CN or —NO 2 ;

A 1 is oxygen;

A 2 is oxygen, NR 2 or CR 7 R 8 ;

G is G-2;

B 1 , B 2 , B 3 , B 4 and B 5 are independently C—R 9 ;

Y is hydrogen, halogen, —CN; or Y is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, or heterocyclyl or heteroaryl each of which is unsubstituted or substituted with one or more of halogen, hydroxy, amino, alkyl- or di(alkyl)amino, alkyl, cycloalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, R 7 S(O)—, R 7 S(O) 2 —, R 7 C(O)—, R 7 R 8 NC(O)—, R 7 OC(O)—, R 7 C(O)O—, R 7 C(O)NR 8 —, —CN or —NO 2 ; or Y is Y-1, Y-2, Y-3, Y-4, Y-5, Y-6, Y-7, Y-8, Y-9, Y-10, Y-11, Y-12 or Y-13;

R 2 , R 3 are independently hydrogen, alkyl, haloalkyl, thioalkyl, alkylthioalkyl, hydroxyalkyl, alkoxylakyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, R 10 S(O)—, R 10 S(O) 2 —, R 10 C(O)—, R 10 C(S)—, R 10 R 11 NC(O)—, R 10 R 11 NC(S)— R 10 OC(O)—;

R 4 , R 5 and R 6 are independently hydrogen, alkyl, haloalkyl, thioalkyl, alkylthioalkyl, hydroxyalkyl, alkoxylakyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, aryl or heteroaryl;

R 7 and R 8 are independently hydrogen, alkyl, haloalkyl, thioalkyl, alkylthioalkyl, hydroxyalkyl, alkoxylakyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl;

R 9 is hydrogen, halogen, —CN, or alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, halocycloalkyl, alkylcycloalkyl or cycloalkylalkyl, each which is unsubstituted or substituted with one or more of halogen, hydroxy, amino, alkyl- or di(alkyl)amino, alkyl, cycloalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, R 7 S(O)—, R 7 S(O) 2 —, R 7 C(O)—, R 7 R 8 NC(O)—, R 7 OC(O)—, R 7 C(O)O—, R 7 C(O)NR 8 —, —CN or —NO 2 ;

R 10 , R 11 , R 12 and R 13 are each independently hydrogen, alkyl, haloalkyl, thioalkyl, alkylthioalkyl, hydroxyalkyl, alkoxylakyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl; or

R 10 together with R 11 form ═O, ═S or ═NR 2 ; or

R 12 together with R 13 form ═O, ═S or ═NR 2 ;

W is O, S or NR 2 ;

n is 1-4; and

m is 0, 1 or 2.

2. The compound of claim 1 , wherein A 2 is CR 7 R 8 .

3. The compound of claim 1 , wherein:

R 1 is halogen, alkyl or haloalkyl; and

X is optionally substituted aryl.

4. The compound of claim 1 , wherein:

X is optionally substituted aryl;

R 1 is halogen, alkyl or haloalkyl; and

Y is Y-1, Y-2, Y-3, Y-4, Y-5, Y-6, Y-7, Y-8, Y-9, Y-10, Y-11, Y-12 or Y-13.

5. The compound of claim 1 , wherein:

X is optionally substituted aryl;

R 1 is halogen, alkyl or haloalkyl; and

Y is pyrazolyl or triazolyl.

6. The compound of claim 1 , wherein:

R 1 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

X is phenyl, which may be unsubstituted or substituted by one or more halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

A 2 is CR 7 R 8 ;

Y is Y-1, Y-4, Y-5, Y-6;

R 3 and R 4 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 akoxy-C 1 -C 4 alkyl or C 1 -C 4 alkylthio-C 1 -C 4 alkyl;

R 2 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; and

R 9 is hydrogen, halogen, —CN, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.

7. The compound of claim 6 , wherein:

A 2 is CH 2 ;

R 9 is hydrogen;

R 12 together with R 13 form ═O, ═S or ═NR 2 ;

R 3 and R 4 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl; and

R 2 is hydrogen.

8. The compound of claim 6 , wherein:

A 2 is CH 2 ;

R 9 is hydrogen;

R 10 together with R 11 form ═O, ═S or ═NR 2 ;

R 3 and R 4 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl; and

R 2 is hydrogen.

9. The compound of claim 6 , wherein:

A 2 is CH 2 ;

R 9 is hydrogen;

R 12 together with R 13 form ═O, ═S or ═NR 2 ;

R 3 and R 4 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl; and

R 2 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.

10. The compound of claim 6 , wherein:

A 2 is CH 2 ,

R 9 is hydrogen;

R 10 together with R 11 form ═O, ═S or ═NR 2 ;

R 3 and R 4 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl; and

R 2 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.

11. The compound of claim 6 , wherein:

A 2 is CH 2 ;

R 9 is hydrogen;

R 10 together with R 11 form ═O, ═S or ═NR 2 ;

R 12 together with R 13 form ═O, ═S or ═NR 2 ; and

R 3 and R 4 are independently hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.

12. A veterinary parasiticidal composition comprising an effective amount of a compound of formula (I) of claim 1 in combination with a pharmaceutically acceptable carrier.

13. A composition for the protection of crops, plants, plant propagation material or material made from wood from pests comprising a pesticidally effective amount of a compound of formula (I) of claim 1 in combination with an agriculturally acceptable carrier or diluent.

14. The composition of claim 12 , wherein the composition comprises an additional active agent.

15. The composition of claim 14 , wherein the additional active agent is an arylpyrazole compound, an amino acetonitrile active agent, another isoxazoline active agent, a paraherquamide active agent, a benzimidazole, an imidazothiazole, a tetrahydropyrimidine active agent, an antitrematodal active agent, a macrocyclic lactone, an insect growth regulator, a neonicotinoid active agent, a pyrethroid, a formamidine or a spinosyn active agent.

16. The composition of claim 15 , wherein the macrocyclic lactone is abamectin, dimadectin, doramectin, emamectin, eprinomectin, ivermectin, latidectin, lepimectin, selamectin, milbemectin, milbemycin D, moxidectin, nemadectin or milbemycin oxime.

17. The compound of claim 1 , wherein A 2 is oxygen.

18. The compound of claim 17 , wherein:

R 1 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

X is phenyl, which may be unsubstituted or substituted by one or more halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

Y is Y-1, Y-4, Y-5, Y-6;

R 3 and R 4 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 akoxy-C 1 -C 4 alkyl or C 1 -C 4 alkylthio-C 1 -C 4 alkyl; and

R 2 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; and

R 9 is hydrogen, halogen, —CN, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.

19. The compound of claim 1 , wherein A 2 is NR 2 .

20. The compound of claim 19 , wherein:

R 1 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

X is phenyl, which may be unsubstituted or substituted by one or more halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

Y is Y-1, Y-4, Y-5, Y-6;

R 3 and R 4 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 akoxy-C 1 -C 4 alkyl or C 1 -C 4 alkylthio-C 1 -C 4 alkyl;

R 2 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; and

R 9 is hydrogen, halogen, —CN, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.

21. The compound of claim 2 , wherein:

R 1 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

X is phenyl, which may be unsubstituted or substituted by one or more halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

Y is Y-2, Y-3, Y-7, Y-8 or Y-9;

R 2 , R 3 , R 4 , R 7 , R 8 are each independently hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; and

R 9 is hydrogen, halogen, —CN, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.

22. The compound of claim 21 , wherein:

Y is Y-7, Y-8 or Y-9;

R 1 is C 1 -C 4 haloalkyl;

R 2 , R 3 , R 4 , R 7 , R 8 and R 9 are hydrogen;

R 10 together with R 11 form ═O, ═S or ═NR 2 ; and

R 12 together with R 13 form ═O, ═S or ═NR 2 .

23. The compound of claim 2 , wherein:

R 1 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

X is phenyl, which may be unsubstituted or substituted by one or more halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

Y is Y-10, Y-11, Y-12 or Y-13;

R 9 is hydrogen, halogen, —CN, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; and

R 10 and R11 are independently hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; or R 10 together with R 11 form ═O, ═S or ═NR 2 ; and

W is O or S.

24. The compound of claim 2 , wherein:

R 1 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

X is phenyl, which may be unsubstituted or substituted by one or more halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

Y is Y-4 or Y-5;

R 3 and R 4 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 akoxy-C 1 -C 4 alkyl or C 1 -C 4 alkylthio-C 1 -C 4 alkyl;

R 2 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

R 7 and R 8 are independently hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; and

R 9 is hydrogen, halogen, —CN, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.

25. The compound of claim 24 , wherein:

R 1 is C 1 -C 4 haloalkyl;

X is phenyl substituted by one or more halogen or C 1 -C 4 haloalkyl;

Y is Y-4;

R 2 is hydrogen, methyl or CF 3 ;

R 3 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

R 7 and R 8 are hydrogen;

R 9 is hydrogen, chloro, fluoro, methyl or CF 3 ;

R 10 together with R 11 form ═O, ═S or ═NR 2 ; and

R 12 and R 13 are independently hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl, or R 12 together with R 13 form ═O, ═S or ═NR 2 .

26. The compound of claim 25 , wherein:

R 1 is CF 3 ;

X is phenyl substituted by one or more chloro, fluoro or CF 3 ;

R 2 and R 9 are hydrogen;

R 3 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;

R 10 together with R 11 form ═O, ═S or ═NR 2 ;

R 12 together with R 13 form ═O, ═S or ═NR 2 ; and

n is 1 or 2.

27. The compound of claim 26 , wherein:

X is phenyl substituted by one or more chloro or CF 3 ;

R 3 is CH 2 CF 3 ;

R 10 together with R 11 form ═O;

R 12 together with R 13 form ═O; and

n is 1.

28. The compound of claim 24 , wherein:

R 1 is C 1 -C 4 haloalkyl;

X is phenyl substituted by one or more halogen or C 1 -C 4 haloalkyl;

Y is Y-5;

R 2 is hydrogen, methyl or CF 3 ;

R 4 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 thioalkyl;

R 7 and R 8 are hydrogen;

R 9 is hydrogen, chloro, fluoro, methyl or CF 3 ;

R 10 together with R 11 form ═O, ═S or ═NR 2 ; and

R 12 and R 13 are independently hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl, or R 12 together with R 13 form ═O, ═S or ═NR 2 .

29. The compound of claim 28 , wherein:

R 1 is CF 3 ;

X is phenyl substituted by one or more chloro, fluoro or CF 3 ;

R 2 and R 9 are hydrogen;

R 4 is C 1 -C 4 thioalkyl;

R 10 together with R 11 form ═O;

R 12 and R 13 are hydrogen; and

n is 1 or 2.

30. A dihydroazole compound of formula (IIa), or pharmaceutically or agriculturally acceptable salt thereof:

wherein Z, B 1 , B 2 , B 3 , B 4 , B 5 , R 15 , R 16 and p are selected from:

Compound

No.

(Z) p

B 5

B 4

B 3

B 2

B 1

R 15

R 16

1.001

3,5-Cl 2

C—H

C—H

C—H

C—H

N

H

CH 2 C(O)NHCH 2 CF 3

1.002

3,5-Cl 2

C—H

C—H

C—H

C—H

N

H

CH 2 CF 3

1.003

3,5-(CF 3 ) 2

C—H

C—H

C—H

C—H

N

CH 3

CH 2 CO 2 CH 3

1.004

3,5-(CF 3 ) 2

C—H

C—H

C—H

C—H

N

CH 3

CH 2 CO 2 H

1.005

3,5-(CF 3 ) 2

C—H

C—H

C—H

C—H

N

CH 3

CH 2 C(O)NHCH 2 CF 3

1.006

3,5-(CF 3 ) 2

C—H

C—H

C—H

C—H

N

H

CH 2 C(O)NHCH 2 CF 3

1.007

3,5-(CF 3 ) 2

C—H

C—H

C—H

C—H

N

H

CH 2 CH 2 SCH 3

1.008

3,5-(CF 3 ) 2

C—H

C—H

C—H

C—H

C—H

H

CH 2 C(O)NHCH 2 CF 3

1.009

3,5-(CF 3 ) 2

C—H

C—H

C—H

C—H

C—H

H

CH 2 CH 2 SCH 3

1.010

3,5-(CF 3 ) 2

C—H

C—H

C—H

C—H

C—H

H

CH 2 CF 3

1.011

3,5-Cl 2

C—H

C—H

C—H

C—H

C—H

H

CH 2 C(O)NHCH 2 CF 3

1.012

3,5-Cl 2

C—H

C—H

C—H

C—H

C—H

H

CH 2 CF 3

1.013

3,5-Cl 2

C—H

C—H

C—H

C—H

C—H

H

CH 2 CH 2 SCH 3

1.014

3-Cl,5-CF 3

C—H

C—H

C—H

C—H

C—H

H

CH 2 C(O)NHCH 2 CF 3

1.015

3-Cl,5-CF 3

C—H

C—H

C—H

C—H

C—H

H

CH 2 CF 3

1.016

3-Cl,5-CF 3

C—H

C—H

C—H

C—H

C—H

H

CH 2 CH 2 SCH 3

1.017

3,5-Cl 2

C—H

C—H

C—Me

C—H

C—Me

H

CH 2 C(O)NHCH 2 CF 3

1.018

3,5-Cl 2

C—H

C—H

C—Me

C—H

C—Me

H

CH 2 CF 3

1.019

3,5-Cl 2

C—H

C—H

C—Me

C—H

C—Me

H

CH 2 CH 2 SCH 3

1.020

3,5-(CF 3 ) 2

C—H

C—H

C—Me

C—H

C—Me

H

CH 2 C(O)NHCH 2 CF 3

1.021

3,5-(CF 3 ) 2

C—H

C—H

C—Me

C—H

C—Me

H

CH 2 CF 3

1.022

3,5-(CF 3 ) 2

C—H

C—H

C—Me

C—H

C—Me

H

CH 2 CH 2 SCH 3

1.023

3-Cl,5-CF 3

C—H

C—H

C—Me

C—H

C—Me

H

CH 2 C(O)NHCH 2 CF 3

1.024

3-Cl,5-CF 3

C—H

C—H

C—Me

C—H

C—Me

H

CH 2 CF 3

1.025

3-Cl,5-CF 3

C—H

C—H

C—Me

C—H

C—Me

H

CH 2 CH 2 SCH 3 .

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 16, 2016
From: MERIAL LIMITED
To: MERIAL, INC.
Reel/Frame 039038/0884 →
CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNMENT DOCUMENTATION PREVIOUSLY RECORDED ON REEL 026376 FRAME 0202. ASSIGNOR(S) HEREBY CONFIRMS THE CORRECT PRIORITY APPLICATION NUMBER LISTED IN THE ASSIGNMENT. Recorded Jul 16, 2014
From: DE FALLOIS, LOIC PATRICK LE HIR; LEE, HYOUNG IK; WILKINSON, DOUGLAS EDWARD; BECK, BRENT CHRISTOPHER
To: MERIAL LIMITED
Reel/Frame 033341/0808 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 2, 2011
From: DE FALLOIS, LOIC PATRICK LE HIR; LEE, HYOUNG IK; WILKINSON, DOUGLAS EDWARD; BECK, BRENT CHRISTOPHER
To: MERIAL LIMITED
Reel/Frame 026376/0202 →