Chemical compounds, process for their preparation and use thereof
Disclosed are compounds of formula (I) or pesticidally acceptable salts thereof wherein, for example, W is ═CR 8 — or ═C(NR 9 R 10 )—, R 8 is halogen, R 9 and R 10 are independently of one another hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, aralkyl or heterocyclylalkyl, R 1 is cyano, methyl, trifluoromethyl or —CS—NH 2 , R 2 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, R 3 is hydrogen, alkyl or cycloalkyl, R 4 and R 5 are alkenyl, alkynyl or cycloalkyl, R 6 is haloalkyl, haloalkoxy, halogen or —SF 5 , R 7 is halogen or alkyl, and n is 0, 1 or 2. These compounds can be used for controlling pests, especially by treatment of domestic animals.
1. A compound of formula I or a pesticidally acceptable salt thereof, wherein
W is ═CR 8 — or ═C(NR 9 R 10 )—,
R 8 is halogen, alkyl or haloalkyl,
R 9 and R 10 are independently of one another hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl,
which groups R 9 and R 10 independently of one another are optionally substituted by one or more halogen, C 3 -C 7 -cycloalkyl, aryl, heteroaryl, C 1 -C 6 -alkoxy and/or C 1 -C 6 -haloalkoxy,
R 1 is cyano, methyl, trifluoromethyl, —CS—NH 2 or —C(═NR 11 )S(O) n R 12 ,
R 11 is hydrogen, alkyl or aryl,
R 12 is alkyl or aryl,
which groups R 11 and/or R 12 are optionally substituted by one or more halogen, hydroxyl, oxo, nitro, cyano, amino, alkyl, alkoxy, alkylthio, cycloalkyl, aryl, heterocyclyl and/or aralkyl groups,
R 2 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl or C 2 -C 6 -haloalkynyl,
R 3 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, heterocyclyl, aralkyl or heterocyclylalkyl, which group R 3 is optionally substituted by one or more halogen, hydroxyl, cyano, nitro, carboxy, carboxylic acid ester, oxo, alkylcarbonyl, haloalkylcarbonyl, cycloalkylcarbonyl, alkylcycloalkylcarbonyl, arylcarbonyl, aralkylcarbonyl, heterocyclylcarbonyl, heterocyclylalkylcarbonyl, amino, alkyl, alkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, alkylthio, haloalkylthio, cycloalkylthio, alkylcycloalkylthio, arylthio, aralkylthio, heterocyclylthio, heterocyclyl-alkylthio, alkylsulphoxidyl, haloalkylsulphoxidyl, cycloalkylsulphoxidyl, alkylcycloalkylsulphoxidyl, arylsulphoxidyl, aralkylsulphoxidyl, heterocyclylsulphoxidyl, heterocyclylalkylsulphoxidyl, alkylsulphonyl, haloalkylsulphonyl, cycloalkylsulphonyl, alkylcycloalkyl-sulphonyl, arylsulphonyl, aralkylsulphonyl, heterocyclylsulphonyl, heterocyclylalkylsulphonyl, cycloalkyl, cycloalkyloxy, aryl, aryl substituted by one or more halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano, nitro, alkylthio, haloalkylthio, cycloalkylthio, alkylcycloalkylthio, arylthio, aralkylthio, heterocyclylthio, heterocyclylalkylthio, alkylsulphoxidyl, haloalkylsulphoxidyl, cycloalkylsulphoxidyl, alkylcycloalkylsulphoxidyl, arylsulphoxidyl, aralkylsulphoxidyl, heterocyclylsulphoxidyl, heterocyclylalkylsulphoxidyl, alkylsulphonyl, haloalkylsulphonyl, cycloalkylsulphonyl, alkylcycloalkylsulphonyl, arylsulphonyl, aralkylsulphonyl, heterocyclylsulphonyl, heterocyclylalkylsulphonyl, and/or amino groups, heterocyclyl, heterocyclyl substituted by one or more halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, cycloalkylthio, alkylcycloalkylthio, arylthio, aralkylthio, heterocyclylthio, heterocyclylalkylthio, alkylsulphoxidyl, haloalkylsulphoxidyl, cycloalkylsulphoxidyl, alkylcycloalkylsulphoxidyl, arylsulphoxidyl, aralkylsulphoxidyl, heterocyclylsulphoxidyl, heterocyclylalkylsulphoxidyl, alkylsulphonyl, haloalkylsulphonyl, cycloalkylsulphonyl, alkylcycloalkyl-sulphonyl, arylsulphonyl, aralkylsulphonyl, heterocyclylsulphonyl, heterocyclylalkylsulphonyl, hydroxy and/or oxo groups, aralkyl and/or heterocyclylalkyl group,
R 4 and R 5 are independently of one another hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, heterocyclyl, aralkyl or heterocyclylalkyl or R 4 and R 5 together with the attached C-atom form a four- to seven-membered saturated or unsaturated ring which optionally contains oxygen, sulfur and/or nitrogen atoms in the ring and/or which is fused to one or more saturated or unsaturated carbocyclic or heterocyclic ring, which groups R 4 and/or R 5 or which ring formed by R 4 and R 5 are optionally substituted by one or more halogen, hydroxyl, cyano, nitro, carboxy, carboxylic acid ester, oxo, alkylcarbonyl, haloalkylcarbonyl, cycloalkylcarbonyl, alkylcycloalkylcarbonyl, arylcarbonyl, aralkylcarbonyl, heterocyclylcarbonyl, heterocyclylalkylcarbonyl, amino, alkyl, alkoxy, cycloalkyloxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, alkylthio, haloalkylthio, cycloalkylthio, alkylcycloalkylthio, arylthio, aralkylthio, heterocyclylthio, heterocyclylalkylthio, alkylsulphoxidyl, haloalkylsulphoxidyl, cycloalkylsulphoxidyl, alkylcycloalkylsulphoxidyl, arylsulphoxidyl, aralkylsulphoxidyl, heterocyclylsulphoxidyl, heterocyclylalkylsulphoxidyl, alkylsulphonyl, haloalkylsulphonyl, cycloalkylsulphonyl, alkylcycloalkyl-sulphonyl, arylsulphonyl, aralkyl-sulphonyl, heterocyclylsulphonyl, heterocyclylalkylsulphonyl, cycloalkyl, aryl, aryl substituted by one or more halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano, nitro, alkylthio, haloalkylthio, cycloalkylthio, alkylcycloalkylthio, arylthio, aralkylthio, heterocyclylthio, heterocyclylalkylthio, alkylsulphoxidyl, haloalkylsulphoxidyl, cycloalkylsulphoxidyl, alkylcycloalkylsulphoxidyl, arylsulphoxidyl, aralkylsulphoxidyl, heterocyclylsulphoxidyl, heterocyclylalkylsulphoxidyl, alkylsulphonyl, haloalkylsulphonyl, cycloalkylsulphonyl, alkylcycloalkylsulphonyl, arylsulphonyl, aralkylsulphonyl, heterocyclylsulphonyl, heterocyclylalkylsulphonyl, and/or amino groups, heterocyclyl, heterocyclyl substituted by one or more halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, cycloalkylthio, alkylcycloalkylthio, arylthio, aralkylthio, heterocyclylthio, heterocyclylalkylthio, alkylsulphoxidyl, haloalkylsulphoxidyl, cycloalkylsulphoxidyl, alkylcycloalkylsulphoxidyl, arylsulphoxidyl, aralkylsulphoxidyl, heterocyclylsulphoxidyl, heterocyclylalkylsulphoxidyl, alkylsulphonyl, haloalkylsulphonyl, cycloalkylsulphonyl, alkylcycloalkyl-sulphonyl, arylsulphonyl, aralkylsulphonyl, heterocyclylsulphonyl, heterocyclylalkylsulphonyl, hydroxy and/or oxo groups, aralkyl and/or heterocyclylalkyl group,
R 6 is haloalkyl, haloalkoxy, halogen or —SF 5 ,
R 7 is halogen, alkyl or —NR 17 R 18 ,
R 17 and R 18 are independently of one another hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl or C 2 -C 6 -alkynyl, which groups R 17 and/or R 18 are optionally substituted by one or more halogen, C 3 -C 7 -cycloalkyl, aryl, heteroaryl, C 1 -C 6 -alkoxy or C 1 -C 6 -haloalkoxy, and
n is 0, 1, or 2.
2. A compound as claimed in claim 1 , wherein W is ═C(R 8 )— and R 8 is halogen or haloalkyl or a pesticidally acceptable salt thereof.
3. A compound as claimed in claim 2 , wherein R 8 is chlorine or fluorine or a pesticidally acceptable salt thereof.
4. A compound as claimed in claim 1 , wherein R 1 is cyano, methyl, trifluoromethyl or —CS—NH 2 or a pesticidally acceptable salt thereof.
5. A compound as claimed in claim 4 , wherein R 1 is —CN or —CS—NH 2 or a pesticidally acceptable salt thereof.
6. A compound as claimed in claim 1 , wherein R 2 is (C 1 -C 3 )-haloalkyl, preferably chlorine and —CF 3 or a pesticidally acceptable salt thereof.
7. A compound as claimed in claim 1 , wherein R 3 is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl or haloalkynyl or a pesticidally acceptable salt thereof.
8. A compound as claimed in claim 1 or a pesticidally acceptable salt thereof, wherein R 3 is hydrogen or (C 1-C 6 )-alkyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 6 )-alkoxy, (C 1 -C 6 )-haloalkoxy, (C 3 -C 6 )-alkenyloxy, (C 3 -C 6 )-haloalkenyloxy, (C 3 -C 6 )-alkynyloxy, (C 3 -C 6 )-aloalkynyloxy, (C 3 -C 7 )-cycloalkyl, S(O) p R 19 , CN, NO 2 , OH, R 20 , R 21 , COR 19 , NR 22 R 23 , OR 19 , COOH and CO 2 R 19 , wherein R 19 , R 20 , R 21 , R 22 , R 23 and p are as defined in claim 14 .
9. A compound as claimed in claim 8 , wherein R 3 is hydrogen or (C 1 -C 3 )-alkyl or a pesticidally acceptable salt thereof.
10. A compound as claimed in claim 1 , wherein R 4 and R 5 independently of one another are alkenyl, alkynyl, haloalkenyl or haloalkynyl or a pesticidally acceptable salt thereof.
11. A compound as claimed in claim 1 , wherein R 4 and R 5 are independently of one another (C 2 -C 6 )-alkenyl, (C 2 -C 6 )-haloalkenyl, (C 2 -C 6 )-alkynyl, (C 2 -C 6 )-haloalkynyl, (C 3 -C 7 )-cycloalkyl, (C 3 -C 7 )-cycloalkyl-(C 1 -C 4 )-alkyl, or are independently of one another phenyl, heterocyclyl which are unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 6 )-alkoxy, (C 1 -C 6 )-haloalkoxy, (C 3 -C 6 )-alkenyloxy, (C 3 -C 6 )-haloalkenyloxy, (C 3 -C 6 )-alkynyloxy, (C 3 -C 6 )-haloalkynyloxy, (C 3 -C 7 )-cycloalkyl, (C 3 -C 7 )-cycloalkyloxy, S(O) P R 19 , CN, NO 2 , OH, R 20 , R 21 , COR 19 , NR 22 R 23 , OR 19 , COOH and CO 2 R 19 ,
or are each independently (C 1 -C 6 )-alkyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 6 )-alkoxy, (C 1 -C 6 )-haloalkoxy, (C 3 -C 6 )-alkenyloxy, (C 3 -C 6 )-haloalkenyloxy, (C 3 -C 6 )-alkynyloxy, (C 3 -C 6 )-haloalkynyloxy, (C 3 -C 7 )-cycloalkyl, (C 3 -C 7 )-cycloalkyloxy, S(O) P R 19 , CN, NO 2 , OH, R 20 , R 21 , COR 19 , NR 22 R 23 , COOH and CO 2 R 19 , or
R 4 and R 5 together with the attached C atom can form a four- to seven-membered saturated ring or a five- to seven-membered unsaturated ring, which optionally contains one or more hetero atoms in the ring which are selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals, selected from the group consisting of halogen, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-haloalkyl and oxo, and when present any additional ring N atom is unsubstituted or substituted by a (C 1 -C 6 )-alkyl, CO—(C 1 -C 6 )-alkyl or CH 2 R 20 radical; or which is condensed with a benzene ring, wherein R 19 , R 20 , R 21 , R 22 , R 23 and p are as defined in claim 14 or a pesticidally acceptable salt thereof.
12. A compound as claimed in claim 1 , wherein R 6 is halogen, (C 1 -C 3 )-alkyl, (C 1 -C 3 )-haloalkyl or —SF 5 , preferably chlorine or —CF 3 or a pesticidally acceptable salt thereof.
13. A compound as claimed in claim 1 , wherein R 7 and R 8 are halogen or R 7 is —NR 17 R 18 or a pesticidally acceptable salt thereof.
14. A compound as claimed in claim 1 , wherein
R 1 is —CN,
R 7 is halogen, —CH 3 or —NR 17 R 18 ,
R 6 is (C 1 -C 3 )-haloalkyl, (C 1 -C 3 )-haloalkoxy or —SF 5 ,
R 3 is hydrogen, (C 2 -C 6 )-alkenyl, (C 2 -C 6 )-haloalkenyl, (C 2 -C 6 )-alkynyl, (C 2 -C 6 )-haloalkynyl, (C 3 -C 7 )-cycloalkyl, (C 3 -C 7 )-cycloalkyl-(C 1 -C 6 )-alkyl, or (C 1 -C 6 )-alkyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 6 )-alkoxy, (C 1 -C 6 )-haloalkoxy, (C 3 -C 6 )-alkenyloxy, (C 3 -C 6 )-haloalkenyloxy, (C 3 -C 6 )-alkynyloxy, (C 3 -C 6 )-haloalkynyloxy, (C 3 -C 7 )-cycloalkyl, (C 3 -C 7 )-cycloalkyloxy, —S(O) P R 19 , —CN, —NO 2 , —OH, R 20 , R 21 , —COR 19 , —NR 22 R 23 , —OR 19 , —COOH and —CO 2 R 19 , R 2 is (C 1 -C 6 )-alkyl, (C 1 -C 6 )-haloalkyl, (C 2 -C 6 )-alkenyl, (C 2 -C 6 )-haloalkenyl, (C 2 -C 6 )-alkynyl or (C 2 -C 6 )-haloalkynyl,
R 4 and R 5 are each independently (C 2 -C 6 )-alkenyl, (C 2 -C 6 )-haloalkenyl, (C 2 -C 6 )-alkynyl, (C 2 -C 6 )-haloalkynyl, (C 3 -C 7 )-cycloalkyl, (C 3 -C 7 )-cycloalkyl-(C 1 -C 4 )-alkyl, or are each independently phenyl, heterocyclyl which are unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 6 )-alkoxy; (C 1 -C 6 )-haloalkoxy, (C 3 -C 6 )-alkenyloxy, (C 3 -C 6 )-haloalkenyloxy, (C 3 -C 6 )-alkynyloxy, (C 3 -C 6 )-haloalkynyloxy, (C 3 -C 7 )-cycloalkyl, (C 3 -C 7 )-cycloalkyloxy, S(O) p R 19 , CN, NO 2 , OH,
R 20 , R 21 , COR 19 , NR 22 R 23 , OR 19 , COOH and CO 2 R 19 , or are each independently (C 1 -C 6 ) -alkyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 6 )-alkoxy, (C 1 -C 6 )-haloalkoxy, (C 3 -C 6 )-alkenyloxy, (C 3 -C 6 )-haloalkenyloxy, (C 3 -C 6 )-alkynyloxy, (C 3 -C 6 )-haloalkynyloxy, (C 3 -C 7 )-cycloalkyl, (C 3 -C 7 )-cycloalkyloxy, S(O) p R 19 , CN, NO 2 , OH, R 20 , R 21 , COR 19 , NR 22 R 23 , COOH and CO 2 R 19 , or
R 4 and R 5 together with the attached C atom can form a four- to seven-membered saturated ring or a five- to seven-membered unsaturated ring, which optionally contains one or more hetero atoms in the ring which are selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-haloalkyl and oxo, and when present any additional ring N atom is unsubstituted of substituted by a (C 1 -C 6 )-alkyl, CO—(C 1 -C 6 )-alkyl or CH 2 R 20 radical; or which is condensed with a benzene ring,
R 19 is (C 1 -C 6 )-alkyl, (C 1 -C 6 )-haloalkyl, (C 3 -C 7 )-cycloalkyl, (C 1 -C 4 )-alkyl-(C 3 -C 7 )-cycloalkyl, —(CH 2 ) q R 20 or —(CH 2 ) q R 21 ,
R 20 is phenyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-haloalkyl, (C 1 -C 6 )-alkoxy, (C 1 -C 6 )-haloalkoxy 3 CN, NO 2 , S(O) q R 19 and NR 22 R 23 ,
R 21 is heterocyclyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkyl, (C 1 -C 4 )-alkoxy, S(O) p R 19 , OH and oxo,
R 22 and R 23 are each independently hydrogen, (C 1 -C 6 )-alkyl or (C 2 -C 6 )-alkenyl, alkynyl, which last three mentioned groups are unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 3 -C 7 )-cycloalkyl, R 20 , R 21 , (C 1-C 6 )-alkoxy, (C 1 -C 6 )-haloalkoxy, and
n and p and q are each independently zero, one or two.
15. A compound as claimed in claim 1 , wherein:
R 1 is CN,
R 7 and R 8 are Cl,
R 6 is CF 3 ,
R 3 is hydrogen or (C 1 -C 3 )-alkyl, and
R 2 is CF 3 .
16. A compound as claimed in claim 1 , wherein:
R 4 R 5 are each independently (C 2 -C 6 )-alkenyl, (C 2 -C 6 )-haloalkenyl, (C 2 -C 6 )-alkynyl, (C 2 -C 6 )-haloalkynyl, (C 3 -C 7 )-cycloalkyl, (C 3 -C 7 )-cycloalkyl-(C 1 -C 4 )-alkyl, or are each independently R 20 , R 21 , unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 6 )-alkoxy, (C 3 -C 6 )-alkenyloxy, (C 3 -C 6 )-haloalkenyloxy, (C 3 -C 6 )-alkynyloxy, (C 3 -C 6 )-haloalkynyloxy, (C 3 -C 7 )-cycloalkyl, S(O) p R 19 , CN, NO 2 , OH, R 20 , R 21 , COR 19 , NR 22 R 23 , OR 19 , COOH and CO 2 R 19 , or are each independently (C 1 -C 6 )-alkyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 6 )-alkoxy, (C 1 -C 6 )-haloalkoxy, (C 3 -C 6 ) -alkenyloxy, (C 3 -C 6 )-haloalkenyloxy, (C 3 -C 6 )-alkynyloxy, (C 3 -C 6 )-haloalkynyloxy, (C 3 -C 7 )-cycloalkyl, S(O) p R 19 , CN, NO 2 , OH, R 20 , R 21 , COR 19 , NR 22 R 23 , OR 19 , COOH and CO 2 R 19 ,
R 4 and R 5 together with the attached C atom can form a four-to seven-membered saturated ring or a five-to seven-membered unsaturated ring, which optionally contains one or more additional hetero atoms in the ring which are selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-haloalkyl and oxo, and when present any additional ring N atom is unsubstituted or substituted by a (C 1 -C 6 )-alkyl, CO—(C 1-C 6 )-alkyl or CH 2 R 20 radical; or which is condensed with a benzene ring, wherein R 19 , R 20 , R 21 , R 22 , R 23 and p are as defined in claim 14 .
17. A process for preparation of a compound of formula I as claimed in claim 1 ,
wherein R 1 is cyano, halogen, alkyl or haloalkyl and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , W and n are as defined in claim 1 , comprising reacting a compound of formula II:
wherein R 1 is cyano, halogen, alkyl or haloalkyl and R 2 , R 3 , R 6 , R 7 , W and n are as defined in claim 1 , with an oxime of formula III, wherein R 4 and R 5 are as defined in claim 1
R 4 R 5 C═N—OH (III) and phosgene or a phosgene precursor in the presence of a base.
18. A process for preparation of a compound of formula I as claimed in claim 1 , wherein R 1 is —CSNH 2 , and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , W and n are as defined in claim 1 , comprising reacting a compound of formula I, wherein R 1 is CN, with alkali or alkaline earth metal hydro sulphides in at inert solvent at a temperature from -35° C. to 50° C.
19. A process for preparation of a compound of formula I as claimed in claim 1 ,
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and W are as defined in claim 1 , and n is 1 or 2 comprising oxidation of a compound of formula I, in which n is 0 or 1.
20. A pesticidal composition comprising as an active ingredient at least one compound of formula I according to claim 1 or a pesticidial acceptable salt thereof.
21. A pesticidal composition according to claim 20 comprising diluents and/or carriers and/or surface active agents which a compatible with said active ingredient.
22. A pesticidal composition according to claim 20 which is a veterinary medicament and which is adapted for oral administration.