Thioamide compounds, method of making and method of using thereof

1. A thioamide compound of formula (Ia):

wherein

R 1 , R 8 , R 9 , R 10 and R 11 , independently of one another, are hydrogen, cyano, nitro, halogen, C 1 -C 6 -alkyl, C 3 -C 7 -cycloalkyl, halo-C 1 -C 6 -alkyl, C 1 -C 6 -alkylthio, halo C 1 -C 6 -alkylthio, C 1 -C 6 -alkylsulfinyl, halo C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -alkylsulfonyl, halo C 1 -C 6 -alkylsulfonyl, SF 5 , arylthio, C 1 -C 6 -alkoxy, C 3 -C 7 -cycloalkyloxy, halo-C 1 -C 6 -alkoxy, C 1 -C 6 -alkylcarbonyl, halo-C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylsulfinyl, halo-C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -alkylamino, di(C 1 -C 6 -alkyl)amino, unsubstituted or substituted aryl, or unsubstituted or substituted phenoxy, whereby the substituents may each be independent of one another and are selected from the group consisting of cyano, nitro, halogen, C 1 -C 6 -alkyl, halo-C 1 -C 6 -alkyl, C 1 -C 6 -alkylthio, halo-C 1 -C 6 -alkylthio, arylthio, C 1 -C 6 -alkoxy, halo-C 1 -C 6 -alkoxy, C 1 -C 6 -alkylcarbonyl, halo-C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylsulfinyl, halo-C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -alkylsulfonyl, halo-C 1 -C 6 -alkylsulfonyl, SF 5 , and methylthioamino;

R 3 , R 4 and R 5 , independently of one another, are hydrogen, halogen, C 1 -C 6 -alkyl, halo-C 1 -C 6 -alkyl; C 3 -C 7 -cycloalkyl that is either unsubstituted or substituted, whereby the substituents may each be independent of one another and are selected from the group consisting of halogen and C 1 -C 6 -alkyl; and phenyl that is either unsubstituted or substituted, whereby the substituents may each be independent of one another and are selected from the group consisting of cyano, nitro, halogen, C 1 -C 6 -alkyl, halo-C 1 -C 6 -alkyl, C 1 -C 6 -alkylthio, halo-C 1 -C 6 -alkylthio, arylthio, C 1 -C 6 -alkoxy, halo-C 1 -C 6 -alkoxy, C 1 -C 6 -alkylcarbonyl, halo-C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylsulfinyl, halo-C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -alkylsulfonyl, halo-C 1 -C 6 -alkylsulfonyl, SF 5 , C 1 -C 6 -alkylamino, and di(C 1 -C 6 -alkyl)amino;

or R 4 and R 5 together signify C 2 -C 6 -alkylene;

R 6 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylthiocarbonyl or benzyl that is either unsubstituted or substituted, whereby the substituents may each be independent of one another and are selected from the group consisting of cyano, nitro, halogen, C 1 -C 6 -alkyl, halo-C 1 -C 6 -alkyl, C 1 -C 6 -alkylthio, halo-C 1 -C 6 -alkylthio, arylthio, C 1 -C 6 -alkoxy, halo-C 1 -C 6 -alkoxy, C 1 -C 6 -alkylcarbonyl, halo-C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylsulfinyl, halo-C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -alkylsulfonyl, halo-C 1 -C 6 -alkylsulfonyl, SF 5 , C 1 -C 6 -alkylamino, and di(C 1 -C 6 -alkyl)amino;

R 7 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylthiocarbonyl, phenyl that is either unsubstituted or substituted, whereby the substituents may each be independent of one another and are selected from the group consisting of cyano, nitro, halogen, C 1 -C 6 -alkyl, halo-C 1 -C 6 -alkyl, C 1 -C 6 -alkylthio, halo-C 1 -C 6 -alkylthio, arylthio, C 1 -C 6 -alkoxy, halo-C 1 -C 6 -alkoxy, C 1 -C 6 -alkylcarbonyl, halo-C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylsulfinyl, halo-C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -alkylsulfonyl, SF 5 , C 1 -C 6 -alkylamino, and di(C 1 -C 6 -alkyl)amino; heteroaryl that is either unsubstituted or substituted, whereby the substituents may each be independent of one another and are selected from the group consisting of cyano, nitro, halogen, C 1 -C 6 -alkyl, halo-C 1 -C 6 -alkyl, C 1 -C 6 -alkylthio, halo-C 1 -C 6 -alkylthio, arylthio, C 1 -C 6 -alkoxy, halo-C 1 -C 6 -alkoxy, C 1 -C 6 -alkylcarbonyl, halo-C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylsulfinyl, halo-C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -alkylsulfonyl, SF 5 , C 1 -C 6 -alkylamino, and di(C 1 -C 6 -alkyl)amino; or naphthyl or quinolyl that is either unsubstituted or substituted, whereby the substituents may each be independent of one another and are selected from the group consisting of cyano, nitro, halogen, C 1 -C 6 -alkyl, halo-C 1 -C 6 -alkyl, C 1 -C 6 -alkylthio, halo-C 1 -C 6 -alkylthio, arylthio, C 1 -C 6 -alkoxy, halo-C 1 -C 6 -alkoxy, C 1 -C 6 -alkylcarbonyl, halo-C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkylsulfinyl, halo-C 1 -C 6 -alkylsulflnyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -alkylamino, and di(C 1 -C 6 -alkyl)amino;

P is C—R 1 or N;

V is C—R 8 or N;

W is C—R 9 or N;

X is C—R 10 or N;

Y is C—R 11 or N;

Z is a direct bond, C(O), C(S) or S(O) p ;

T is independently O, S or NH;

a is 1, 2 or 3; and

p is 1 or 2.

2. The compound of claim 1 , wherein:

R 1 , R 8 , R 9 , R 10 and R 11 , independently of one another, is hydrogen, cyano, chloro or trifluoromethyl;

R 3 , R 4 and R 6 is H;

R 5 is hydrogen, C 1 -C 6 alkyl or halo-C 1 -C 6 -alkyl;

P is N or C—R 1 ;

V is C—R 8 ;

W is C—R 9 ;

X is C—R 10 ;

Y is C—R 11 ;

Z is C(O);

T is O;

R 7 is phenyl that is unsubstituted or substituted, wherein the substituents may each be independent of one another and are selected from the group consisting of halogen, C 1 -C 6 -alkylthio, halo-C 1 -C 6 -alkylthio, C 1 -C 6 -alkoxy, and halo-C 1 -C 6 -alkoxy, and

a is 1.

3. The compound of claim 1 , wherein:

R 1 , R 8 , R 9 , R 10 and R 11 , independently of one another, is hydrogen, cyano, chloro or trifluoromethyl;

R 3 , R 4 and R 6 is H;

R 5 is methyl;

P is C—R 1 ;

V is C—R 8 ;

W is C—R 9 ;

X is C—R 10 ;

Y is C—R 11 ;

Z is C(O);

T is O;

R 7 is phenyl that is unsubstituted or substituted, wherein the substituents may each be independent of one another and are selected from the group consisting of halo-C 1 -C 6 -alkylthio and halo-C 1 -C 6 -alkoxy, and a is 1.

4. The compound of claim 1 , wherein R 5 is C 1 -C 6 -alkyl or halo-C 1 -C 6 -alkyl.

5. The compound of claim 1 , wherein R 3 and R 4 are each independently hydrogen.

6. The compound of claim 4 , wherein R 5 is methyl.

7. The compound of claim 5 , wherein R 5 is methyl.

8. The compound of claim 1 , wherein T is O.

9. The compound of claim 1 , wherein:

T is O;

Z is C(O);

R 3 and R 4 are each hydrogen; and

R 5 is methyl.

10. The compound of claim 3 wherein:

T is O;

Z is C(O);

R 3 , R 4 and R 6 are each hydrogen;

R 5 is methyl; and

R 7 is unsubstituted phenyl or phenyl substituted with —OCF 3 or —SCF 3 .

11. A pesticidal composition comprising an effective amount of a compound of claim 1 and a pesticidally or veterinarily acceptable carrier.

12. The composition of claim 11 which further comprises a pesticidal compound.

13. The composition of claim 12 , wherein the pesticidal compound is an arylpyrazole, a nodulisporic acid, an amino acetonitrile compound, a macrocyclic lactone, an insect growth regulator, or a paraherquamide compound.

14. The composition of claim 13 wherein the arylpyrazole is fipronil; or the macrocyclic lactone is abamectin, dimadectin, doramectin, emamectin, eprinomectin, ivermectin, latidectin, lepimectin, selamectin, milbemectin, milbemycin D, milbemycin oxime, moxidectin, nemadectin, or combinations thereof.

15. A method of producing the compounds of claim 1 , wherein the compounds of formula (Ia) are produced by a process which comprises

(i) reacting a compound of formula (IIa)

with ammonium sulfide wherein R 3 , R 4 , R 5 , R 6 , R 7 , P, Q, V, W, X, Y, Z, a, are as defined above for the compounds of formula (Ia) in a solvent with or without the presence of base.

16. A method of treating an animal against endoparasitic infection by administering an endoparasiticidally effective amount of the compound of claim 1 to an animal in need thereof.

17. The method of claim 16 , wherein the endoparasitic infection is a helminth selected from Anaplocepheda, Ancylostoma, Anecator, Ascaris, Caenorhabditis, Capillaria, Cooperia, Dipyllidinum, Dirofilaria, Echinococcus, Enterobius, Fasciola, Haemonchus, Oesophagostumum, Ostertagia, Toxocara, Strongyloides, Toxascaris, Trichinella, Trichuris, Trichostrongylus and combinations thereof.

18. The method of claim 17 wherein the helminth is Haemonchus contortus.

19. A method of treating an animal against ectoparasitic infection by administering an ectoparasiticidally effective amount of the compound of claim 1 to an animal in need thereof.

20. The method of claim 19 wherein the ectoparasites are selected from fleas, ticks, mites, mosquitoes, flies, lice, blowfly and combinations thereof.

21. The method of claim 19 wherein the ectoparasites are selected from Ctenocephalides, Rhipicephalus, Dermacentor, Ixodes, Boophilus, Ambylomma, Haemaphysalis, Hyalomma, Sarcoptes, Psoroptes, Otodectes, Chorioptes, Hypoderma, Damalinia, Linognathus, Haematopinus, Solenoptes, Trichodectes, Felicola , and combinations thereof.

22. The method of claim 16 or 19 further comprising administering to an animal in need thereof at least one veterinarily active ingredient in addition to the compound of claim 1 .

23. The method of claim 22 wherein the at least one veterinarily active ingredient is an arylpyrazole, a nodulisporic acid, an amino acetonitrile compound, a macrocyclic lactone, an insect growth regulator, an or a paraherquamide compound.

24. The method of claim 23 wherein the arylpyrazole is fipronil; or the macrocyclic lactone is abamectin, dimadectin, doramectin, emamectin, eprinomectin, ivermectin, latidectin, lepimectin, selamectin, milbemectin, milbemycin D, milbemycin oxime, moxidectin, nemadectin, or combinations thereof.