UREA AND THIOUREA SUBSTITUTED BICYCLES DERIVATIVES AS PESTICIDES

Abstract

The present invention relates to compounds of formula (I) a compound of formula (1) as defined herein, to processes for preparing them, to pesticidal, in particular insecticidal, acaricidal, molluscicidal and to combat and control pests such as insect, acarine, mollusc and nematode pests.

##STR00001##

Claims

1. A compound of formula (I) ##STR00105## or a compound of formula (I) ##STR00106## wherein Q is selected from ##STR00107## A.sup.1 is N or CR.sup.A1; A.sup.2 is N or CR.sup.A2; A.sup.3 is N or CR.sup.A3; A.sup.4 is N or CR.sup.A4; A.sup.5 is N or CR.sup.A5; A.sup.6 is N or CR.sup.A6; A.sup.7 is O or S; with the proviso that not more than four of A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are N; R.sup.A1, R.sup.A2, R.sup.A3, R.sup.A4, R.sup.A5 and R.sup.A6 are independently selected from H, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, -(C.sub.0-C.sub.6alkyl)(C.sub.3-6cycloalkyl), C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6haloalkynyl, -(C.sub.0-6alkyl)(C.sub.3-C.sub.6halocycloalkyl), -(C.sub.3-C.sub.6cycloalkyl)(C.sub.1-C.sub.3haloalkyl), -(C.sub.0-6alkyl)-heterocyclyl, -(C.sub.0-C.sub.6alkyl)-heteroaryl, halogen, CN, -C.sub.1-C.sub.4alkyl-CN, -C.sub.3-C.sub.6cycloalkyl-CN, NO.sub.2, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl, S-C.sub.1-C.sub.6alkyl, S(O)-C.sub.1-C.sub.6alkyl, S(O).sub.2 C.sub.1-C.sub.6alkyl, S(O)(NH)C.sub.1-C.sub.6alkyl, NH-C.sub.1-C.sub.6alkyl, N(C.sub.1-C.sub.6alkyl).sub.2, NH-C.sub.3-C.sub.6cycloalkyl, N(C.sub.1-C.sub.6alkyl)(C.sub.3-C.sub.6cycloalkyl), C(O)C.sub.1-C.sub.6alkyl, C(O)H, C(O)C.sub.1-C.sub.6alkoxy, C(O)C.sub.1-C.sub.6haloalkoxy, C(O)NH(C.sub.1-C.sub.6alkyl), C(O)NH(C.sub.1-C.sub.6haloalkyl) and C(O)N(C.sub.1-C.sub.6 alkyl).sub.2; W is NR.sup.1 or O; Y is O or S; J is a 5- or 6-membered heteroaryl or heterocyclyl, wherein said heteroaryl and heterocyclyl is unsubstituted or substituted with one to three substituents independently selected from C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, -(C.sub.0-C.sub.6alkyl)C.sub.3-8cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6haloalkynyl, -(C.sub.0-6alkyl)C.sub.3-8halocycloalkyl, -C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.3haloalkyl, -(C.sub.0-C.sub.6alkyl)heterocyclyl, halogen, CN, -C.sub.1-C.sub.4alkyl-CN, -C.sub.3-C.sub.6cycloalkyl-CN, NO.sub.2, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.4haloalkoxy, -(C.sub.1-C.sub.4alkyl)(C.sub.1-C.sub.4alkoxy), S-C.sub.1-C.sub.6alkyl, S(O)-C.sub.1-C.sub.6alkyl, S(O).sub.2 C.sub.1-C.sub.6alkyl, S(O)(NH)C.sub.1-C.sub.6alkyl, S-C.sub.1-C.sub.6haloalkyl, S(O)-C.sub.1-C.sub.6haloalkyl, S(O).sub.2 C.sub.1-C.sub.6haloalkyl, S(O)(NH)C.sub.1-C.sub.6haloalkyl, NH(C.sub.1-C.sub.6alkyl), N(C.sub.2-C.sub.6alkyl).sub.2, NH(C.sub.3-C.sub.6cycloalkyl), N(C.sub.1-C.sub.6alkyl)(C.sub.3-C.sub.6cycloalkyl), C(O)(C.sub.1-C.sub.6alkyl), CHO, C(O)(C.sub.2-C.sub.6alkoxy), C(O)(C.sub.1-C.sub.6haloalkoxy), C(O)NH(C.sub.1-C.sub.6alkyl), C(O)NH(C.sub.1-C.sub.6haloalkyl) and C(O)N(C.sub.1-C.sub.6alkyl).sub.2; Ar.sup.1 and Ar.sup.2 are independently selected from phenyl and heteroaryl, wherein said phenyl and heteroaryl are unsubstituted or substituted by one to three substituents independently selected from C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, (C.sub.0-C.sub.6alkyl)-C.sub.3-6cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6haloalkynyl, -(C.sub.0-C.sub.6alkyl)C.sub.3-6halocycloalkyl, -C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.3haloalkyl, -(C.sub.0-C.sub.6alkyl)heterocyclyl, halogen, CN, -C.sub.1-C.sub.6alkyl-CN, -C.sub.3-C.sub.6cycloalkyl-CN, NO.sub.2, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6haloalkoxy, -(C.sub.1-C.sub.4alkyl)(C.sub.1-C.sub.4alkoxy), S-C.sub.1-C.sub.6alkyl, S(O)-C.sub.1-C.sub.6alkyl, S(O).sub.2 C.sub.1-C.sub.6alkyl, S(O)(NH)C.sub.1-C.sub.6alkyl, S-C.sub.1-C.sub.6haloalkyl, S(O)-C.sub.1-C.sub.6haloalkyl, S(O).sub.2 C.sub.1-C.sub.6haloalkyl, S(O)(NH)C.sub.1-C.sub.6haloalkyl, NH(C.sub.1-C.sub.6alkyl), N(C.sub.1-C.sub.6alkyl).sub.2, NH(C.sub.3-C.sub.6cycloalkyl), N(C.sub.1-C.sub.6alkyl)(C.sub.3-C.sub.6cycloalkyl), C(O)(C.sub.1-C.sub.6alkyl), CHO, C(O)(C.sub.1-C.sub.6alkoxy), C(O)(C.sub.1-C.sub.1-6haloalkoxy), C(O)NH(C.sub.1-C.sub.6alkyl), C(O)NH(C.sub.1-C.sub.6haloalkyl) and C(O)N(C.sub.1-C.sub.6alkyl).sub.2; R.sup.1 and R.sup.2 are independently selected from H, C.sub.1-C.sub.6 alkyl, C.sub.i C.sub.6 haloalkyl, -(C.sub.0-C.sub.6alkyl)C.sub.3-C.sub.6-cycloalkyl, -(C.sub.0-C.sub.6alkyl)C.sub.3-8halocycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6haloalkynyl, -(C.sub.1-C.sub.4alkyl)O(C.sub.1-C.sub.4alkyl), S-C.sub.1-C.sub.6alkyl, S-C.sub.1-C.sub.6haloalkyl, S(O)-C.sub.1-C.sub.6alkyl, S(O).sub.2-C.sub.1-C.sub.6alkyl, S(O)-C.sub.1-C.sub.6haloalkyl, S(O).sub.2-C.sub.1-C.sub.6haloalkyl, C(O)(C.sub.1-C.sub.6alkyl), C(O)(C.sub.1-C.sub.6alkoxy), C(O)NH(C.sub.1-C.sub.6alkyl), C(O)N(C.sub.1-C.sub.6alkyl).sub.2, OC(O)(C.sub.1-C.sub.6alkoxy), OC(O)NH(C.sub.1-C.sub.6alkyl), OC(O)N(C.sub.1-C.sub.6alkyl).sub.2 and C(N-C.sub.1-C.sub.4alkoxy)-C.sub.1-C.sub.4alkyl; provided that when R.sup.1 and R.sup.2 are different from H, R.sup.1 and R.sup.2 is unsubstituted or substituted by one to three substituents independently selected from C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, halogen, CN, NO.sub.2, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6haloalkoxy, S(O)-C.sub.1-C.sub.6alkyl, S(O).sub.2C.sub.1-C.sub.6alkyl, S(O).sub.2C.sub.1-C.sub.6alkyl, S(O)(NH)C.sub.1-C.sub.6alkyl, NH(C.sub.1-C.sub.6alkyl), N(C.sub.1-C.sub.6alkyl).sub.2, NH(C.sub.3-C.sub.6cycloalkyl), N(C.sub.1-C.sub.4alkyl)(C.sub.3-C.sub.6cycloalkyl), C(O)(C.sub.1-C.sub.6alkyl), C(O)(C.sub.1-C.sub.6alkoxy, C(O)NH(C.sub.1-C.sub.6alkyl) and C(O)(C.sub.1-C.sub.6alkyl); R.sup.3 is selected from H, C.sub.1-C.sub.6 alkyl, -(C.sub.0-6alkyl)C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C(O)H, C(O)(C.sub.1-C.sub.6-alkyl), C(O)O(C.sub.1-C.sub.6-alkyl), C(O)(C.sub.0-6alkyl)(C.sub.3-C.sub.6-cycloalkyl), C(O)O(C.sub.0-6alkyl)(C.sub.3-C.sub.6-cycloalkyl)-C(O)(C.sub.2-C.sub.6-alkenyl), C(O)O(C.sub.2-C.sub.6-alkenyl), -(C.sub.1-C.sub.6-alkyl)O(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)S(C.sub.1-C.sub.6-alkyl), C(O)(C.sub.1-C.sub.6-alkyl)C(O)O(C.sub.1-C.sub.6-alkyl), -(C.sub.0-6alkyl)phenyl, -(C.sub.0-6alkyl)-O-phenyl, C(O)-(C.sub.0-C.sub.6-alkyl)(heteroaryl), C(O)-(C.sub.0-C.sub.6-alkyl)(heterocyclyl), -(C.sub.0-C.sub.6-alkyl)(heteroaryl), -(C.sub.0-C.sub.6-alkyl)(heterocyclyl), -(C.sub.0-C.sub.6-alkyl) -O-(heteroaryl), -(C.sub.0-C.sub.6-alkyl)-O-(heterocyclyl), -(C.sub.1-C.sub.6-alkyl)OC(O)(C.sub.1-C.sub.6-alkyl)-O-(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)OC(O)(C.sub.1-C.sub.6-alkyl)-O-(C.sub.1-C.sub.6-alkyl)-O-(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)OC(O)(C.sub.1-C.sub.6-alkyl)-O-(C.sub.1-C.sub.6-haloalkyl), -(C.sub.1-C.sub.6-alkyl)OC(O)(C.sub.1-C.sub.6-alkyl)-N(R.sup.3a)C(O)O-(C.sub.0-6alkyl)-phenyl, -(C.sub.1-C.sub.6-alkyl)OC(O)(C.sub.1-C.sub.6-alkyl)-N(R.sup.3a)C(O)O-(C.sub.0-6alkyl)-heteroaryl, -(C.sub.1-C.sub.6-alkyl)OC(O)(C.sub.1-C.sub.6-alkyl)-N(R.sup.3a)C(O)O-(C.sub.0-6alkyl)-heterocyclyl, -(C.sub.1-C.sub.6-alkyl)-C(O)N(R.sup.3a)-(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)-C(O)N(R.sup.3a)-(C.sub.0-C.sub.6-alkyl) -heteroaryl-C(O)O-(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)-C(O)N(R.sup.3a)-(C.sub.0-C.sub.6-alkyl) -heterocyclyl-C(O)O-(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)-C(O)N(R.sup.3a)-(C.sub.0-C.sub.6-alkyl)-heteroaryl, -(C.sub.1-C.sub.6-alkyl)-C(O)N(R.sup.3a)-(C.sub.0-C.sub.6-alkyl)-heterocyclyl, -(C.sub.1-C.sub.6-alkyl)-C(O)-heteroaryl, -(C.sub.1-C.sub.6-alkyl)-C(O)-(C.sub.0-C.sub.6-alkyl)heterocyclyl, -(C.sub.1-C.sub.6-alkyl)-C(O)N(R.sup.3a)(C.sub.1-C.sub.6-alkyl)(N(R.sup.3a)(R.sup.3b))(C(O)OH), -(C.sub.1-C.sub.6-alkyl)-C(O)N(R.sup.3a)(C.sub.1-C.sub.6-alkyl)(N(R.sup.3a)(R.sup.3b)), -(C.sub.1-C.sub.6-alkyl)-C(O)N(R.sup.3a)(C.sub.1-C.sub.6-alkyl)N(R.sup.3a)C(O)O-(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)-C(O)N(R.sup.3a)(C.sub.1-C.sub.6-alkyl)N(R.sup.3a)C(O)O-(C.sub.1-C.sub.6-alkyl)(C(O)OH), -(C.sub.1-C.sub.6-alkyl)-C(O)-(C.sub.0-C.sub.6-alkyl)heteroaryl-C(O)O-(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)-C(O)-(C.sub.0-C.sub.6-alkyl)-heterocyclyl-C(O)O-(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl) -OC(O)O-(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)-O-C(O)(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)OC(O)(C.sub.3-C.sub.6-cycloalkyl), -(C.sub.1-C.sub.6-alkyl)-OC(O)-(C.sub.0-C.sub.6-alkyl)heteroaryl, -(C.sub.1-C.sub.6-alkyl)-OC(O)(C.sub.0-C.sub.6-alkyl)heterocyclyl, -(C.sub.1-C.sub.6-alkyl)-OC(O)-(C.sub.1-C.sub.6-alkyl) -N(R.sup.3a)C(O)O-(C.sub.1-C.sub.6-alkyl), -(C.sub.0-C.sub.6-alkyl)-NR.sup.3aR.sup.3b, -(C.sub.1-C.sub.6-alkyl)-O-(C.sub.0-C.sub.6-alkyl)heteroaryl and -(C.sub.1-C.sub.6-alkyl)-O-(C.sub.0-C.sub.6-alkyl)heterocyclyl; wherein each alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, heteroaryl and heterocyclyl are unsubstituted or substituted with one or more substituents independently selected from halogen, CN, NO.sub.2, NR.sup.3aR.sup.3b, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, S-(C.sub.1-C.sub.6-alkyl), S(O)(C.sub.1-C.sub.6-alkyl), S(O).sub.2(C.sub.1-C.sub.6-alkyl), OS(O).sub.2(C.sub.1-C.sub.6-alkyl), OS(O).sub.2(C.sub.1-C.sub.6-haloalkyl), C(O)H, C(O)OH, C(O)NR.sup.3aR.sup.3b, -(C.sub.1-C.sub.6-alkyl)NR.sup.3aR.sup.3b, C(O)(C.sub.1-C.sub.6-alkyl), C(O)O(C.sub.1-C.sub.6-alkyl), C(O)(C.sub.1-C.sub.6-haloalkyl), C(O)O(C.sub.1-C.sub.6-haloalkyl), C(O)(C.sub.3-C.sub.6-cycloalkyl), C(O)O(C.sub.3-C.sub.6-cycloalkyl), C(O)(C.sub.2-C.sub.6-alkenyl), C(O)O(C.sub.2-C.sub.6-alkenyl), -(C.sub.1-C.sub.6-alkyl)O(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)S(C.sub.1-C.sub.6-alkyl), C(O)(C.sub.1-C.sub.6-alkyl)C(O)O(C.sub.1-C.sub.6-alkyl), phenyl, O-phenyl, Si(C.sub.1-C.sub.6-alkyl).sub.3, S(O)NR.sup.3aR.sup.3b, S(O).sub.2NR.sup.3aR.sup.3b, heteroaryl and heterocyclyl; Z is a 4- to 7-membered heterocyclyl or heteroaryl, which heterocyclyl or heteroaryl is unsubstituted or substituted with one or two substituents independently selected from halogen, CN, NO.sub.2, oxo, hydroxy, NR.sup.ZaR.sup.Zb, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, S-(C.sub.1-C.sub.6-alkyl), S(O)(C.sub.1-C.sub.6-alkyl), S(O).sub.2(C.sub.1-C.sub.6-haloalkyl), OS(O).sub.2(C.sub.1-C.sub.6-alkyl), -OS(O).sub.2(C.sub.1-C.sub.6-haloalkyl), C(O)H, C(O)OH, C(O)NR.sup.ZaR.sup.Zb, -(C.sub.1-C.sub.6-alkyl)NR.sup.ZaR.sup.Zb, C(O)(C.sub.1-C.sub.6-alkyl), C(O)O(C.sub.1-C.sub.6-alkyl), C(O)(C.sub.1-C.sub.6-haloalkyl), C(O)O(C.sub.1-C.sub.6-haloalkyl), C(O)(C.sub.3-C.sub.6-cycloalkyl), C(O)O(C.sub.3-C.sub.6-cycloalkyl), C(O)(C.sub.2-C.sub.6-alkenyl), C(O)O(C.sub.2-C.sub.6-alkenyl), -(C.sub.1-C.sub.6-alkyl)O(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)S(C.sub.1-C.sub.6-alkyl), C(O)(C.sub.1-C.sub.6-alkyl)C(O)O(C.sub.1-C.sub.6-alkyl), phenyl, O-phenyl, Si(C.sub.1-C.sub.6-alkyl).sub.3, S(O)NR.sup.ZaR.sup.Zb, S(O).sub.2NR.sup.ZaR.sup.Zb, heteroaryl and heterocyclyl; wherein each alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, heteroaryl and heterocyclyl substituent is unsubstituted or substituted with one or more substituents independently selected from halogen, CN, NO.sub.2, NR.sup.ZaR.sup.Zb, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, S-(C.sub.1-C.sub.6-alkyl), S(O)(C.sub.1-C.sub.6-alkyl), S(O).sub.2(C.sub.1-C.sub.6-alkyl), OS(O).sub.2(C.sub.1-C.sub.6-alkyl), OS(O).sub.2(C.sub.1-C.sub.6-haloalkyl), C(O)H, C(O)OH, C(O)NR.sup.ZaR.sup.Zb, -(C.sub.1-C.sub.6-alkyl)NR.sup.ZaR.sup.Zb, C(O)(C.sub.1-C.sub.6-alkyl), C(O)O(C.sub.1-C.sub.6-alkyl), C(O)(C.sub.1-C.sub.6-haloalkyl), C(O)O(C.sub.1-C.sub.6-haloalkyl), C(O)(C.sub.3-C.sub.6-cycloalkyl), C(O)O(C.sub.3-C.sub.6-cycloalkyl), C(O)(C.sub.2-C.sub.6-alkenyl), C(O)O(C.sub.2-C.sub.6-alkenyl), -(C.sub.1-C.sub.6-alkyl)O(C.sub.1-C.sub.6-alkyl), -(C.sub.1-C.sub.6-alkyl)S(C.sub.1-C.sub.6-alkyl), C(O)(C.sub.1-C.sub.6-alkyl)C(O)O(C.sub.1-C.sub.6-alkyl), phenyl, O-phenyl, Si(C.sub.1-C.sub.6-alkyl).sub.3, S(O)NR.sup.ZaR.sup.Zb, S(O).sub.2NR.sup.ZaR.sup.Zb, heteroaryl and heterocyclyl; R.sup.3a, R.sup.3b, R.sup.Za and R.sup.Zb are independently selected from H, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6-cycloalkyl and C.sub.1-C.sub.6-alkoxy; or an agrochemically acceptable salt, stereoisomer, tautomer, N-oxide thereof.

2. The compound according to claim 1, of formula (Ia) ##STR00108##

3. The compound according to claim 1, of formula (Ib) ##STR00109##

4. The compound according to claim 1, of formula (Ic) ##STR00110##

5. The compound according to claim 1, of formula (Id) ##STR00111##

6. The compound according to claim 1, of formula (Ie) ##STR00112##

7. The compound according to claim 1, of formula (If) ##STR00113##

8. The compound according to claim 1, wherein Q is ##STR00114## W is NH; Y is O or S; R.sup.2 is selected from H, C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl; J is ##STR00115## Ar.sup.1 is phenyl which is unsubstituted or substituted by one to three substituents independently selected from C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, halogen, C.sub.1-C.sub.6alkoxy and C.sub.1-C.sub.6haloalkoxy; Ar.sup.2 is phenyl which is unsubstituted or substituted by one to three substituents independently selected from C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, halogen, C.sub.1-C.sub.4alkoxy and C.sub.1-C.sub.4haloalkoxy; or an agrochemically acceptable salt, stereoisomer, tautomer, N-oxide thereof.

9. A compound according to claim 1, wherein Q is ##STR00116## Y is O or S; J is ##STR00117## Ar.sup.1 is ##STR00118## R.sup.a is selected from C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, halogen, C.sub.1-C.sub.6alkoxy and C.sub.1-C.sub.6haloalkoxy; Ar.sup.2 is ##STR00119## R.sup.b and R.sup.c are independently selected from H, C.sub.1-C.sub.6alkyl and halogen; preferably R.sup.b is C.sub.1-C.sub.6alkyl and R.sup.c is H, more preferably R.sup.b is isopropyl and R.sup.c is H; or an agrochemically acceptable salt, stereoisomer, tautomer, N-oxide thereof.

10. A compound according to claim 1, wherein Q is ##STR00120## Ar.sup.2 is phenyl which is unsubstituted or substituted by one to three substituents independently selected from C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, halogen, C.sub.1-C.sub.4alkoxy and C.sub.1-C.sub.4haloalkoxy; Z is a 4- to 7-membered heterocyclyl or heteroaryl, which heterocyclyl or heteroaryl is unsubstituted or substituted with one or two substituents independently selected from C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4alkoxy, oxo and hydroxy; or an agrochemically acceptable salt, stereoisomer, tautomer, N-oxide thereof.

11. A compound according to claim 1, wherein Q is ##STR00121## Ar.sup.2 is ##STR00122## R.sup.b and R.sup.c are independently selected from H, C.sub.1-C.sub.6alkyl and halogen; preferably R.sup.b is C.sub.1-C.sub.6alkyl and R.sup.c is H, more preferably R.sup.b is isopropyl and R.sup.c is H; Z is a 5 or 6-membered heterocyclyl or heteroaryl, which heterocyclyl or heteroaryl is unsubstituted or substituted with one or two substituents independently selected from C.sub.1-C.sub.6-alkyl, oxo and hydroxy; or an agrochemically acceptable salt, stereoisomer, tautomer, N-oxide thereof.

12. A compound according to claim 1, wherein Q is ##STR00123## Ar.sup.2 is ##STR00124## R.sup.b and R.sup.c are independently selected from H, C.sub.1-C.sub.6alkyl and halogen; preferably R.sup.b is C.sub.1-C.sub.6alkyl and R.sup.c is H, more preferably R.sup.b is isopropyl and R.sup.c is H; Z is a 5-membered heterocyclyl or heteroaryl, which heterocyclyl or heteroaryl is unsubstituted or substituted with one or two substituents independently selected from C.sub.1-C.sub.6-alkyl, oxo and hydroxy; or an agrochemically acceptable salt, stereoisomer, tautomer, N-oxide thereof.

13. A compound according to claim 1, wherein Q is ##STR00125## Ar.sup.2 is ##STR00126## R.sup.b and R.sup.c are independently selected from H, C.sub.1-C.sub.6alkyl and halogen; preferably R.sup.b is C.sub.1-C.sub.6alkyl and R.sup.c is H, more preferably R.sup.b is isopropyl and R.sup.c is H; Z is a 5 or 6-membered heterocyclyl or heteroaryl, which heterocyclyl or heteroaryl is unsubstituted or substituted with one or two substituents independently selected from C.sub.1-C.sub.6-alkyl, oxo and hydroxy; or an agrochemically acceptable salt, stereoisomer, tautomer, N-oxide thereof.

14. A compound according to claim 1, wherein Q is ##STR00127## Ar.sup.2 is ##STR00128## R.sup.b and R.sup.c are independently selected from H, C.sub.1-C.sub.6alkyl and halogen; preferably R.sup.b is C.sub.1-C.sub.6alkyl and R.sup.c is H, more preferably R.sup.b is isopropyl and R.sup.c is H; Z is a 5-membered heterocyclyl or heteroaryl, which heterocyclyl or heteroaryl is unsubstituted or substituted with one or two substituents independently selected from C.sub.1-C.sub.6-alkyl, oxo and hydroxy; or an agrochemically acceptable salt, stereoisomer, tautomer, N-oxide thereof.

15. A pesticidal composition, which comprises at least one compound according to claim 1, or an agrochemically acceptable salt, stereoisomer, tautomer, N-oxide thereof, as active ingredient and at least one auxiliary.

16. The composition according to claim 15, which further comprises one or more other insecticidally, acaricidally, nematicidally and/or fungicidally active agents.

17. A method for controlling pests, which comprises applying a composition according to claim 15 to the pests or their environment with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.

18. method for the protection of plant propagation material from the attack by pests, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition according to claim 15.

19. A coated plant propagation material, wherein the coating of the plant propagation material comprises a compound as defined in claim 1.

Description

EXAMPLE 1

Preparation of 1-(2-isopropylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]thiourea (compound P1.4)

[0182] ##STR00048##

Step A-1: Preparation of 2-oxo-1H-quinoline-6-carbonitrile

[0183] ##STR00049##

[0184] To a solution of 6-bromo-1H-quinolin-2-one (20.0 g, 89.0 mmol) in NMP (80 mL) was added CuCN (12.8 g, 142 mmol) followed by heating the reaction mixture at 150 C. for 16 h. The reaction mixture was cooled to room temperature, poured on to crushed ice, resulted solids filtered, and dried under vacuum to afford 2-oxo-1H-quinoline-6-carbonitrile (15.0 g) as brown solid.

[0185] .sup.1H NMR (300 MHz, DMSO-d.sub.6): 12.15 (s, 1H), 8.24 (s, 1H), 7.91 (d, 2H), 7.41 (s, 1H), 6.63 (s, 1H).

[0186] MS (method D) m/z: 171.1 [M+H].sup.+.

Step A-2: Preparation of 2-chloroquinoline-6-carbonitrile

[0187] ##STR00050##

[0188] A suspension of 2-oxo-1H-quinoline-6-carbonitrile (15.0 g, 88.0 mmol) in POCl.sub.3 (130 mL) was heated at 120 C. for 16 h. The reaction mixture was cooled to room temperature, poured on to crushed ice, resulted solids filtered and dried under vacuum to afford 2-chloroquinoline-6-carbonitrile (14.0 g) as brown solid.

[0189] .sup.1H NMR (300 MHz, DMSO-d.sub.6): 8.73 (s, 1H), 8.57 (d, 1H), 8.09-8.16 (m, 2H), 7.78 (d, 1H).

[0190] MS (method D) m/z:189.1 [M+H].sup.+.

Step A-3: Preparation of tert-butyl N-(6-cyano-2-quinolyl)carbamate

[0191] ##STR00051##

[0192] A suspension of 2-chloroquinoline-6-carbonitrile (14.0 g, 75.0 mmol) in 1, 4 dioxane (230 mL) was charged with tert-butyl carbamate (9.60 g, 82.0 mmol) and NaOH (4.46 g, 116 mmol) at room temperature followed by degassing with argon for 10 min. Pd(OAc).sub.2 (0.50 g, 0.75 mmol) and Xanthphos (0.86 g, 1.48 mmol) were added to the reaction mixture and heated at 100 C. for 16 h. The reaction mixture was cooled to room temperature, filtered through celite bed, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography to afford tert-butyl N-(6-cyano-2-quinolyl)carbamate (10.0 g) as an off white solid.

[0193] .sup.1H NMR (300 MHz, CDCl.sub.3): 8.26 (d, 1H), 8.13-8.18 (m, 2H), 8.04 (s, 1H), 7.84 (d, 1H), 7.78 (d, 1H), 7.75 (d, 1H), 1.51 (s, 9H).

[0194] MS (method D) m/z: 270.1 [M+H].sup.+.

Step A-4: Preparation of tert-butyl N-(6-carbamoyl-2-quinolyl)carbamate

[0195] ##STR00052##

[0196] A solution of tert-butyl N-(6-cyano-2-quinolyl)carbamate (7.00 g, 26.0 mmol) in DMSO (70 mL) was charged with K.sub.2CO.sub.3 (3.50 g) followed by H.sub.2O.sub.2 (21.0 mL) dropwise at 0 C. over 10 min. The reaction mixture was heated to room temperature and stirred for 2 h. The reaction mixture was cooled to 0 C., quenched with ice cold water (400 mL), resulted solids were filtered and dried under vacuum to afford tert-butyl N-(6-carbamoyl-2-quinolyl)carbamate (7.10 g) as an off white solid.

[0197] .sup.1H NMR (300 MHz, DMSO-d.sub.6): 10.26 (s, 1H), 8.43 (d, 1H), 8.35 (d, 1H), 8.09-8.13 (m, 1H), 7.77 (d, 1H), 7.47 (s, 1H),

[0198] MS (method D) m/z:288.1 [M+H].sup.+.

Step A-5: Preparation of tert-butyl N-[6-[(E)-dimethylaminomethylenecarbamoyl]-2-quinolyl]carbamate

[0199] ##STR00053##

[0200] A suspension of tert-butyl N-(6-carbamoyl-2-quinolyl)carbamate (7.10 g, 25.0 mmol) in DMFDMA (35 mL) was heated at 90 C. for 4 h. The reaction mixture was cooled to room temperature and concentrated under reduced pressure to afford tert-butyl N-[6-[(E)-dimethylaminomethylenecarbamoyl]-2-quinolyl]carbamate (7.50 g, crude) as an off white solid.

[0201] .sup.1H NMR (300 MHz, DMSO-d.sub.6): 10.23 (s, 1H), 8.72 (t, 2H), 8.36-8.46 (m, 2H), 8.09(d, 1H), 7.76 (d, 1H), 3.22 (d, 6H), 1.50 (s, 9H).

[0202] MS (method D) m/z: 343.1 [M+H].sup.+.

Step A-6: Preparation of tert-butyl N-[6-(1H-1,2,4-triazol-3-yl)-2-quinolyl]carbamate

[0203] ##STR00054##

[0204] A solution of tert-butyl N-[6-[(E)-dimethylaminomethylenecarbamoyl]-2-quinolyl]carbamate (7.50 g, 19.7 mmol) in acetic acid (75 mL) was charged with hydrazine hydrate (1.00 mL, 19.7 mmol) over 10 min at room temperature. The reaction mixture was heated at 80 C. for 1 h. The reaction mixture was concentrated under reduced pressure, triturated with MTBE (100 mL) and was dried under vacuum to afford to afford tert-butyl N-[6-(1H-1,2,4-triazol-3-yl)-2-quinolyl]carbamate (4.00 g) as an off-white solid.

[0205] .sup.1H NMR (300 MHz, DMSO-d.sub.6): 10.22 (s, 1H), 8.52 (d, 2H), 8.41 (d, 1H), 8.30 (dd, 1H), 8.08 (d, 1H), 7.83 (d, 1H), 1.50 (s, 9H).

[0206] MS (method D) m/z: 312.1 [M+H].sup.+.

Step A-7: Preparation of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinolin-2-amine

[0207] ##STR00055##

[0208] A solution of tert-butyl N-[6-(1H-1,2,4-triazol-3-yl)-2-quinolyl]carbamate (4.00 g, 12.8 mmol) in DMF: water (80 mL, 4:1) was charged with compound 1-iodo-4-(trifluoromethoxy)benzene (3.70 g, 12.8 mmol), Cs.sub.2CO.sub.3 (8.32 g, 25.6 mmol) and 8-hydroxy quinoline (0.43 g, 2.90 mol) and the mixture was degased with argon for 10 min. Cul (0.73 g, 3.80 mol) was added to the reaction mixture and heated at 150 C. for 16 h. The reaction mixture was cooled to room temperature, quenched with water (300 mL) and extracted with EtOAc (2300 mL). The combined organic layers were washed with water (100 mL) and brine (100 mL), dried over anhydrous Na.sub.2SO.sub.4, and concentrated under reduced pressure. The residue was purified by column chromatography to afford 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinolin-2-amine (2.90 g) as an off white solid.

[0209] .sup.1H NMR (300 MHz, DMSO-d.sub.6): 9.41 (s, 1H), 8.39 (d, 1H), 8.20 (d, 1H), 8.03-8.18 (d, 3H), 7.63 (d, 2H), 7.55 (d, 1H), 6.81 (d, 1H), 6.63 (s, 1H).

[0210] MS (method D) m/z: 371.9 [M+H].sup.+.

Step A-8: Preparation of 1-(2-isopropylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]thiourea

[0211] ##STR00056##

[0212] A suspension of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinolin-2-amine (200 mg, 0.54 mmol) in THF (6.0 mL) was charged with NaH (32 mg, 0.81 mmol, 60% in mineral oil) in portions wise at 0 C. and stirred for 30 minutes. A solution of 1-isopropyl-2-isothiocyanato-benzene (477 mg, 2.69 mmol) in THF (6 mL) was added to the reaction mixture and allowed stirred at 60 C. for 16 h. The reaction mixture was cooled to 0 C., quenched with water (10 mL) and extracted with EtOAc (250 mL). The combined organic layers were washed with water (20 mL) and brine (20 mL), dried over anhydrous Na.sub.2SO.sub.4, and concentrated under reduced pressure. The residue was purified by flash column chromatography to afford 1-(2-isopropylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]thiourea (55.0 mg) as an off white solid.

[0213] .sup.1H NMR (300 MHz, DMSO-d.sub.6): 13.81 (s, 1H), 11.30 (s, 1H), 9.47 (s, 1H), 8.67 (d, 1H), 8.55 (d, 1H), 8.39 (d, 1H), 8.11 (d, 2H), 7.92 (d, 1H), 7.64 (d, H), 7.51 (d, 2H), 7.43 (d, 1H), 7.25-7.30 (m,2H), 3.18-3.27 (m, 1H), 1.26 (d, 6H).

[0214] MS (method D) m/z: 548.9 [M+H].sup.+.

EXAMPLE 2

Preparation of 1-(2-isopropylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]1-1,2,4-triazol-3-yl]-2-quinolyl]urea (compound P1.3)

[0215] ##STR00057##

[0216] A solution of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinolin-2-amine (100 mg, 0.269 mmol, example 1, step A-7) in CH.sub.3CN (5.0 mL) was charged with K.sub.2CO.sub.3 (111 mg, 0.81 mmol) and a solution of 1-isocyanato-2-isopropyl-benzene (52 mg, 0.322 mmol) in CH.sub.3CN (5.0 mL). The reaction mixture was stirred at room temperature for 16 h. The resulted solids were filtered and dried under vacuum to afford 1-(2-isopropylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]urea (50 mg) as an off white solid.

[0217] .sup.1H NMR (300 MHz, DMSO-d.sub.6): 11.59 (s, 1H), 10.26 (s, 1H), 9.47 (s, 1H), 8.63 (s, 1H), 8.45-8.49 (m, 2H), 8.09-8.17 (q, 2H), 8.10 (dd, 1H), 7.86 (d, 1H), 7.64 (d, 2H), 7.39 (d, 2H), 7.12-7.7.27 (m, 2H), 3.50-3.54 (m, 1H), 1.34 (d, 6H).

[0218] MS (method D) m/z: 532.8 [M+H].sup.+.

EXAMPLE 3

Preparation of 3-(2-isopropylphenyl)-N-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinoly]1-1,3-thiazetidin-2-imine (compound P2.1)

[0219] ##STR00058##

[0220] A solution of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinolin-2-amine (100 mg, 0.269 mmol, example 1, step A-7) in butan-2-one (5.0 mL) was charged with diiodomethane (0.122 g, 0.456 mmol) and K.sub.2CO.sub.3 (0.202 g, 1.458 mmol). The reaction mixture was stirred at 55 C. overnight. After cooling, the solution was diluted with dichloromethane. The organic phase was washed with sodium thiosulfate and brine, dried over MgSO.sub.4, filtered and evaporated. The crude product was purified by column chromatography to give 3-(2-isopropylphenyl)-N-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]-1,3-thiazetidin-2-imine (60 mg) as a solid (mp: 102-3 C.).

[0221] .sup.1H NMR (400 MHz, CDCl.sub.3): 8.60 (s, 1H), 8.53 (d, 1H), 8.42 (dd, 1H), 8.06 (d, 1H), 7.96 (d, 1H), 7.82 (m, 2H), 7.35-7.42 (m, 4H), 7.35 (t, 1H), 7.22 (m, 1H), 7.10 (d, 1H), 5.01 (s, 2H), 3.33 (sept, 1H), 1.28 (d, 6H).

[0222] LC/MS (method B) m/z: 561 [M+H].sup.+, R.sub.t=2.47 min.

EXAMPLE 4

Preparation of 3-(2-isopropylphenyl)-4-methyl-N-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]thiazol-2-imine (compound P2.2)

[0223] ##STR00059##

[0224] A solution of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinolin-2-amine (200 mg, 0.365 mmol, example 1, step A-7) in butan-2-one (5.0 ml) was charged with triethylamine (0.105 ml, 0.729 mmol) and chloropropan-2-one (0.036 ml, 0.456 mmol). The mixture was stirred at RT for 24h. The solution was diluted with dichloromethane. The organic phase was washed with water, dried over MgSO.sub.4, filtered and evaporated. The crude product was purified by column chromatography to give 3-(2-isopropylphenyl)-4-methyl-N-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-q uinolyl]thiazol-2-imine (58 mg) as a solid.

[0225] .sup.1H NMR (400 MHz, CDCl.sub.3): 8.60 (s, 1H), 8.50 (s, 1H), 8.41 (dd, 1H), 8.08 (d, 1H), 7.92 (d, 1H), 7.85 (d, 2H), 7.51 (m, 2H), 7.35-7.45 (m, 3H), 7.17 (t, 1H), 7.00 (d, 1H), 6.21 (s, 1H), 2.59 (sept, 1H), 1.21 and 1.15 (2d, 6H), 1.14 (d, 6H).

[0226] LC/MS (method B) m/z: 587 [M+H].sup.+, R.sub.t=2.26 min.

EXAMPLE 5

Preparation of (2Z)-3-(2-isopropylphenyl)-2-[[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]imino]thiazolidin-4-one (compound P2.3) and (2E)-2-(2-isopropylphenyl)imino-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]thiazolidin-4-one (compound P2.4)

[0227] ##STR00060##

[0228] A solution of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinolin-2-amine (200 mg, 0.365 mmol, example 1, step A-7) in butan-2-one (5.0 mL) was charged with triethylamine (0.105 ml, 0.729 mmol) and chloracetyl chloride (0.052 g, 0.456 mmol). The mixture was stirred at 60 C. for 6h. The solution was diluted with dichloromethane. The organic phase was washed with water, dried over MgSO.sub.4, filtered and evaporated. The crude mixture was purified by column chromatography to give (2Z)-3-(2-isopropylphenyl)-2-[[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]imino]thiazolidin-4-one (60 mg, compound P2.3) and (2E)-2-(2-isopropylphenyl)imino-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]thiazolidin-4-one (35 mg, compound P2.4).

[0229] (2Z)-3-(2-isopropylphenyl)-2-[[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]imino]thiazolidin-4-one (compound P2.3)

[0230] .sup.1H NMR (400 MHz, CDCl.sub.3): 8.63 (s, 1H), 8.61 (s, 1H), 8.52 (dd, 1H), 8.10-8.14 (m, 2H), 7.85 (d, 2H), 7.51 (m, 2H), 7.43 (m, 2H), 7.38 (m, 1H), 7.20 (m, 1H), 7.14 (d, 1H), 4.03 (s, 2H), 2.87 (sept, 1H), 1.24 (m, 6H).

[0231] LC/MS (method B) m/z: 589 [M+H].sup.+, R.sub.t=2.30 min.

[0232] (2E)-2-(2-isopropylphenyl)imino-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-quinolyl]thiazolidin-4-one (compound P2.4)

[0233] .sup.1H NMR (400 MHz, CDCl.sub.3): 8.77 (s, 1H), 8.66 (s, 1H), 8.62 (dd, 1H), 8.49 (d, 1H), 8.25 (d, 1H), 7.85 (m, 2H), 7.57 (d, 1H), 7.43 (d, 2H), 7.26 (t, 1H), 7.11-7.15 (m, 2H), 6.89 (d, 1H), 4.10 (s, 2H), 2.99 (sept, 1H), 1.16 (d, 6H).

[0234] LC/MS (method B) m/z: 589 [M+H].sup.+, R.sub.t=2.24 min.

EXAMPLE 6

Preparation of 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinazolin-2-yl]thiourea (component P2.5) and 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)-phenyl]-1,2,4-triazol-3-yl]quinazolin-2-yl]urea (component P2.6)

[0235] ##STR00061##

Step B-1: Preparation of 3-bromo-1[4-(trifluoromethoxy)phenyl]-1,2,4-triazole

[0236] ##STR00062##

[0237] To a mixture of 1-iodo-4-(trifluoromethoxy)benzene (3 g, 10.416 mmol) in methylsulfinylmethane (24 mL) was added 3-bromo-1H-1,2,4-triazole (3.1 g) under nitrogen atmosphere followed by addition of cesium carbonate (6.7 g, 20.833 mmol) and copper iodide (0.4 g, 2.083 mmol). The reaction mass was stirred at 130 C. for 18 hours in seal tube. The reaction mass was then diluted with water and extracted with ethylacetate (370 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the title compound as solid (3 g).

[0238] .sup.1H NMR (400 MHz, (CD.sub.3).sub.3S0): 9.38-9.25 (m, 1H), 7.98-7.92 (m, 2H), 7.65-7.53 (m, 2H)

[0239] LC/MS (method E) m/z: 308 [M+H].sup.+, R.sub.t=0.94 min.

Step B-2: Preparation of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinazolin-2-amine

[0240] ##STR00063##

[0241] In a two neck RB to a solution of 6-bromoquinazolin-2-amine (1.5 g, 6.695 mmol) in 1,4-Dioxane (20 mL) was added potassium acetate(1.0 g, 10.042 mmol) and 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane(2.6 g, 10.042 mmol). The reaction mixture was degassed with nitrogen for 20 min followed by addition of Pd(PPh.sub.3).sub.2Cl.sub.2 (231 mg, 0.335 mmol). The reaction mixture was again degassed for 10 min and then refluxed at 100 C. for overnight.

[0242] Reaction mass was diluted with water and extracted by DCM (350 mL). The combined organic layers were dried over anhydrous sodium sulphate and concentrated under reduced pressure and purified by column chromatography to obtain the title compound as solid (700 mg). .sup.1H NMR (400 MHz, (CD.sub.3).sub.3SO: 9.20-9.14 (m, 1H), 8.17 (s, 1H), 7.86 (br d, 1H), 7.43-7.29 (m, 1H), 7.08-6.98 (m, 2H), 1.32 (s, 12H).

[0243] LC/MS (method F) m/z: 272 [M+H].sup.+, R.sub.t=1.12 min.

Step B-3: Preparation of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinazolin-2-amine

[0244] ##STR00064##

[0245] A mixture of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinazolin-2-amine (100 mg, 0.3689 mmol) and 3-bromo-1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazole (110 mg, 0.3689 mmol)) in 1,4-Dioxane (2 mL) was added sodium bicarbonate (90 mg, 1.107 mmol) dissolved in water (1 mL) followed by addition of Pd(PPh.sub.3).sub.2Cl.sub.2 (25 mg, 0.0368 mmol;). Reaction mixture was then degassed for 10 min and cooked in microwave at 150 C. for 1 hour after which the reaction mixture was poured in water and and extracted with ethyl acetate (320 mL). The combined organic layer were dried over anhydrous sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the title compound as solid (190mg).

[0246] .sup.1H NMR (400 MHz, (CD.sub.3).sub.3SO: 9.48-9.39 (m, 1H), 9.28 (s, 1H), 8.54 (d, 1H), 8.43-8.34 (m, 1H), 8.14-8.04 (m, 2H), 7.71-7.60 (m, 2H), 7.54 (d, 1H), 7.11-6.96 (m, 2H)

[0247] LC/MS (method E) m/z: 373 [M+H].sup.+, R.sub.t=0.75 min.

Step B-4: Preparation of 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinazolin-2-yl]thiourea (component P2.5) and 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinazolin-2-yl]urea (Component P2.6)

[0248] To a stirring solution of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinazolin-2-amine (300 mg, 0.8058 mmol) in tetrahydrofuran (6 mL) under nitrogen atmosphere was added sodium hydride (50 mg, 1.612 mmol) at 0 C. followed by 2-isothiocyanato-1,3-dimethyl-benzene (0.4 mL, 2.417 mmol) and reaction was refluxed at 60 C. for 3 hours. Reaction mass was then diluted with water and extracted with ethyl acetate (325 mL). Combined organic layers were then dried over anhydrous sodium sulphate and concentrated under reduced pressured followed by column chromatography of the crude compound to obtain the two title compounds as solids (150 mg and 70 mg respectively)

Compound P2.5

[0249] ##STR00065##

[0250] .sup.1H NMR (400 MHz, (CD.sub.3).sub.3SO: 2.26 (s, 6H), 7.17 (s, 3H), 7.66 (d, 2H), 8.08-8.19 (m, 3H), 8.62 (d, 1H), 8.84 (s, 1H), 9.51 (s,1H), 9.73 (s, 1H), 11.34 (s, 1H), 12.85 (s, 1H)

[0251] LC/MS (method F) m/z: 536 [M+H].sup.+, R.sub.t=1.72 min.

Compound P2.6

[0252] ##STR00066##

[0253] .sup.1H NMR (400 MHz, (CD.sub.3).sub.3SO: 2.30 (s, 6H), 7.15 (s, 3H), 7.66 (d, 2H), 8.07 (d1H), 8.13 (d, 2H), 8.60 (d, 1H), 8.81 (s, 1H), 9.51 (s, 1H), 9.68 (s, 1H), 10.44 (s, 1H), 11.12 (s, 1H)

[0254] LC/MS (method F) m/z: 520 [M+H].sup.+, R.sub.t=1.68 min.

EXAMPLE 7

Preparation of (2Z)-3-(2,6-dimethylphenyl)-4-methyl-2-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinazolin-2-yl]imino-thiazolidin-4-ol (compound P2.7)

[0255] ##STR00067##

[0256] To the mixture of 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinazolin-2-yl]thiourea (60 mg, 0.112 mmol), methyl ethyl ketone (4 mL), triethylamine (0.05 mL, 0.3361 mmol) and tetrahydrofuran (1 mL) was addedl-chloropropan-2-one (0.03 mL, 0.2241 mmol). The reaction mass was then heated at 60 C. for overnight in a sealed tube. The reaction mass was then diluted with water and extracted with DCM (315 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the title compound as solid (20 mg).

[0257] .sup.1H NMR (400 MHz, (CD.sub.3).sub.3SO: 1.45 (s, 3H), 2.21 (s, 3H), 2.40 (s, 3H), 3.40 (d, 1H), 3.62 (d, 1H), 7.24-7.33 (m, 3H), 7.67 (d, 2H), 7.94 (d, 1H), 8.13 (d, 2H), 8.62 (d, 1H), 8.74 (s, 1H), 9.41 (s, 1H), 9.52 (s, 1H)

[0258] LC/MS (method E) m/z: 592 [M+H].sup.+, R.sub.t=1.12 min.

EXAMPLE 8

Preparation of 3-(2,6-dimethylphenyl)-N-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinazolin-2-yl]-1,3-thiazetidin-2-imine (compound P2.8)

[0259] ##STR00068##

[0260] A suspension of 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinazolin-2-yl]thiourea (400 mg, 0.747 mmol), butan-2-one (15 mL), tetrahydrofuran (3 mL), potassium carbonate (600 mg, 3.735 mmol) and di-iodomethane (0.2 mL, 1.494 mmol) was heated at 60 C. for overnight. The reaction mass was then diluted with water and extracted with DCM (325 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the title compound as solid (120 mg).

[0261] .sup.1H NMR (400 MHz, CDCl.sub.3: 2.40 (s, 6H), 4.92 (s, 2H), 7.03-7.13 (m, 2H), 7.17 (d, 1H), 7.42 (d, 2H), 7.79-7.98 (m, 3H), 8.56-8.67 (m, 3H), 9.32 (s, 1H)

[0262] LC/MS (method F) m/z: 548 [M+H].sup.+, R.sub.t=1.70 min.

EXAMPLE 9

Preparation of (2Z)-3-(2,6-dimethylphenyl)-2-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinazolin-2-yl]imino-thiazolidin-4-one(compound P2.9) and (2Z)-2-(2,6-dimethyl-phenyl)imino-3-[7-[1-[4-(trifluoromethoxy)phenyl]-1,2,4- triazol-3-yl]quinazolin-2-yl]thiazolidin-4-one (compound P2.10)

[0263] ##STR00069##

[0264] In a 2 neck round bottom flask equipped with a two way stopcock and a condenser was added 1-(2,6-dimethylphenyl) -3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinazolin-2-yl]thiourea (200 mg, 0.3735 mmol) methyl ethyl ketone (4 mL), THF (5 ml), triethylamine (0.2 mL, 1.120 mmol) and 2-chloroacetyl chloride (0.44 ml, 0.4482 mmol) one after the other. Reaction was allowed to stir for 30 min at room temperature and then heated at 70 C. for overnight. The reaction mass was then diluted with water and extracted with DCM (325 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the two title compounds both as solids (46 mg and 27 mg respectively)

Compound P2.9

[0265] ##STR00070##

[0266] .sup.1H NMR (400 MHz, CDCl.sub.3: 2.18 (s, 6H), 4.09 (s, 2H), 6.90-6.95 (m, 1H), 6.98-7.03 (m, 2H), 7.43 (d, 2H), 7.85 (d, 2H), 8.25 (d, 1H), 8.66 (s, 1H), 8.82-8.92 (m, 2H), 9.67 (s, 1H)

[0267] LC/MS (method F) m/z: 576 [M+H].sup.+, R.sub.t=1.67 min.

Compound P2.10

[0268] ##STR00071##

[0269] .sup.1H NMR (400 MHz, CDCl.sub.3: 2.23 (s, 6 H,) 4.05 (s, 2 H), 7.16-7.22 (m, 2 H), 7.27-7.30 (m, 1 H), 7.38-7.46 (m, 2 H), 7.80-7.88 (m, 2 H), 8.02-8.09 (m, 1 H), 8.61-8.76 (m, 3 H), 9.39-9.47 (m, 1 H)

[0270] LC/MS (method F) m/z: 576 [M+H].sup.+, R.sub.t=1.67 min.

EXAMPLE 10

Preparation of 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinoxalin-2-yl]thiourea (compound P2.11)

[0271] ##STR00072##

Step C-1: Preparation of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinoxalin-2-amine

[0272] ##STR00073##

[0273] To the solution of tert-butyl N-(6-bromoquinoxalin-2-yl)carbamate (400 mg, 1.234 mmol) in 1,4-Dioxane (10 mL) was added potassium acetate(180 mg, 2.008 mmol) and 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (442 mg, 1.851 mmol). To the reaction mixture was then added Pd(PPh.sub.3).sub.2Cl.sub.2 (110 mg, 0.0617 mmol) and it was refluxed at 100 C. for overnight. The reaction mass was then diluted with water and extracted with dichloromethane (325 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the title compound as solid (125 mg).

[0274] .sup.1H NMR (400 MHz, CDCl.sub.3: 1.39 (s, 12H), 5.19 (br. s, 2H), 7.63 (d, 1H), 7.92-8.03 (m, 1H), 8.35 (s, 1H), 8.41 (s, 1H)

[0275] LC/MS (method E) m/z: 272 [M+H].sup.+, R.sub.t=0.77 min.

Step C-2: Preparation of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinoxalin-2-amine

[0276] ##STR00074##

[0277] A mixture of 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinoxalin-2-amine (250 mg, 0.9222 mmol), 1,4-Dioxane (4 mL), 3-bromo-1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazole (283 mg, 0.922 mmol), sodium bicarbonate solution(230 mg, 2.767 mmol in 1 mL water) was degassed with nitrogen for 20 min and then was added Pd(PPh.sub.3).sub.2Cl.sub.2 (64 mg, 0.0922 mmol) .Reaction was again degassed for 10 min and then was cooked in microwave at 140 C. for 1 hour. The reaction mass was then diluted with water and extracted with ethylacetate (325 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the title compound as solid (80 mg).

[0278] .sup.1H NMR (400 MHz, (CD.sub.3).sub.3SO: 9.48-9.38 (m, 1H), 8.50-8.43 (m, 1H), 8.36 (s, 1H), 8.26 (dd, 1H), 8.15-8.05 (m, 2H), 7.69-7.60 (m, 3H), 7.23-7.13 (m, 2H)

[0279] LC/MS (method E) m/z: 373 [M+H].sup.+, R.sub.t=0.82 min.

Step C-3: Preparation of 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinoxalin-2-yl]thiourea (compound P2.11)

[0280] ##STR00075##

[0281] To a stirring solution of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinoxalin-2-amine (350 mg, 0.9401 mmol) in tetrahydrofuran (16 mL) under nitrogen atmosphere was added sodium hydride (150 mg, 3.760 mmol) at 0 C. followed by 2-isothiocyanato-1,3-dimethyl-benzene (0.6 mL, 3.760 mmol). The reaction mixture was then heated at 60 C. for 3 hours. The reaction mass was then diluted with water and extracted with ethylacetate (325 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the title compound as solid (325 mg).

[0282] .sup.1H NMR (400 MHz, (CD.sub.3).sub.3SO: 2.27 (s, 6H), 7.10-7.33 (m, 3H), 7.64 (d, 2H), 8.04-8.16 (m, 2H), 8.16-8.30 (m, 1H), 8.44 (dd, 1H), 8.63 (d, 1H), 8.96 (s, 1H), 9.49 (s, 1H), 11.65 (s, 1H), 12.56-12.83 (m, 1H)

[0283] LC/MS (method E) m/z: 534 [M+H].sup.+, R.sub.t=1.14 min.

EXAMPLE 11

Preparation of 3-(2,6-dimethylphenyl)-N-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinoxalin-2-yl]-1,3-thiazetidin-2-imine (compound P2.12)

[0284] ##STR00076##

[0285] To a mixture of 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]quinoxalin-2-yl]thiourea (250 mg, 0.4669 mmol), butan-2-one (15 mL) and potassium carbonate (380 mg, 2.334 mmol) was added di-iodomethane (0.12 mL, 0.9337 mmol). The reaction mixture was then heated at 60 C. for overnight. The reaction mass was then diluted with water and extracted with ethylacetate (320 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the title compound as solid (130 mg).

[0286] .sup.1H NMR (400 MHz, CDCl.sub.3: 2.43 (s, 6H), 5.01 (s, 2H), 7.17 (m, 2H), 7.27 (m, 1H), 7.43 (d, 2H), 7.86 (d, 2H), 7.97(d, 1H), 8.50 (dd, 1H), 8.59 (s, 1H), 8.64 (s, 1H), 8.82 (d, 1H)

[0287] LC/MS (method E) m/z: 548 [M+H].sup.+, R.sub.t=1.18 min.

EXAMPLE 12

Preparation of 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-1 ,3-benzothiazol-2-yl]urea (compound P2.16) and 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-1,3-benzothiazol-2-yl]thiourea (compound P2.17)

[0288] ##STR00077##

Step D-1: Preparation of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-benzothiazol-2-amine

[0289] ##STR00078##

[0290] To the stirring solution of 6-bromo-1,3-benzothiazol-2-amine (5 g, 21.825 mmol) in 1,4-Dioxane (80 mL) was added potassium acetate (3 g, 32.737 mmol) and 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (8.3 g, 32.737 mmol). The reaction mixture was degassed with nitrogen for 20 min followed by addition of Pd(PPh.sub.3).sub.2Cl.sub.2 (850 mg, 1.0912 mmol). The reaction mixture was again degassed for 10 min and then refluxed at 100 C. for overnight. The reaction mass was then diluted with water and extracted with dichloromethane (3100 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the title compound as solid (5 g).

[0291] .sup.1H NMR (400 MHz, CDCl.sub.3: 1.35 (s, 12H), 5.45 (br. s, 2H), 7.53 (d, 1H), 7.75 (d, 1H), 8.06 (s, 1H)

[0292] LC/MS (method E) m/z: 277 [M+H].sup.+, R.sub.t=0.96 min.

Step D-2: Synthesis of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-1,3-benzothiazol-2-amine

[0293] ##STR00079##

[0294] To a solution of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-benzothiazol-2-amine (1 g, 3.621 mmol) in 1,4-Dioxane (12 mL) was added 3-bromo-1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazole (1.11 g, 3.621 mmol) and sodium bicarbonate solution(900 mg, 10.86 mmol in 3 mL water). Then reaction mixture was degassed with nitrogen, followed by addion of Pd(PPh.sub.3).sub.2Cl.sub.2 (250 mg, 0.3621 mmol) and was degassed again for 10min. The reaction mass was then diluted with water and extracted with ethylacetate (350 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the title compound as solid (350 mg).

[0295] LC/MS (method E) m/z: 378 [M+H].sup.+, R.sub.t=1.05 min.

Step D-3: Preparation of 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-1,3-benzothiazol-2-yl]urea (compound P2.16) and 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-1,3-benzothiazol-2-yl]thiourea (compound P2.17)

[0296] ##STR00080##

[0297] To a stirring solution of 6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-1,3-benzothiazol-2-amine (350 mg, 0.9276 mmol) in tetrahydrofuran (6 mL) under nitrogen atmosphere was added sodium hydride (180 mg, 3.711 mmol) at 0 C. followed by addition of 2-isothiocyanato-1,3-dimethyl-benzene (0.8 mL, 4.638 mmol). The reaction mixture was then heated at 60 C. for overnight. The reaction mass was then diluted with water and extracted with ethylacetate (330 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the two title compounds both as solids (115 mg and 145 mg respectively).

Compound P2.16

[0298] ##STR00081##

[0299] .sup.1H NMR (400 MHz, (CD.sub.3).sub.3SO: 2.24 (s, 6H), 7.13 (s, 3H), 7.64 (d, 2H), 7.79 (d, 1H), 8.06-8.18 (m, 3H), 8.37 (br. s., 1H), 8.63 (s, 1H), 9.42 (s, 1H), 11.02 (s, 1H)

[0300] LC/MS (method E) m/z: 525 [M+H].sup.+, R.sub.t=1.21 min.

Compound P2.17

[0301] ##STR00082##

[0302] .sup.1H NMR (400 MHz, CDCl.sub.3: 2.40 (s, 6H), 7.20-7.27 (m, 3H), 7.43 (d, 2H), 7.80-7.86 (m, 3H), 8.32 (d, 1H), 8.62 (s, 2H)

[0303] LC/MS (method E) m/z: 541 [M+H].sup.+, R.sub.t=1.25 min.

EXAMPLE 13

Preparation of 3-(2,6-dimethylphenyl)-N-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-1,3-benzothiazol-2-yl]-1,3-thiazetidin-2-imine(compound P2.14) and N-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-1,3-benzothiazol-2-yl]-1,3-thiazetidin-2-imine (compound P2.15)

[0304] ##STR00083##

[0305] To a mixture of 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-1,3-benzothiazol-2-yl]thiourea (300 mg, 0.5549 mmol), butan-2-one (15 mL) and tetrahydrofuran (3 mL) was added potassium carbonate (450 mg, 2.775 mmol) and di-iodomethane (0.13 mL, 1.110 mmol). The reaction mixture was the heated at 60 C. for overnight. The reaction mass was then diluted with water and extracted with ethylacetate (330 mL). The combined organic layers were then dried over sodium sulphate and concentrated under reduced pressure followed by column chromatography to obtain the two title compounds both as solids (15 mg and 20 mg respectively).

Compound P2.14

[0306] ##STR00084##

[0307] .sup.1H NMR (400 MHz, CDCl.sub.3: 2.40 (s, 6H), 4.92 (s, 2H), 7.10-7.17 (m, 2H), 7.19-7.26 (m, 1H), 7.40 (d, 2H), 7.83 (dd, 3H), 8.15-8.25 (m, 1H), 8.51-8.60 (m, 2H)

[0308] LC/MS (method F) m/z: 553 [M+H].sup.+, R.sub.t=1.79 min.

Compound P2.15

[0309] ##STR00085##

[0310] .sup.1H NMR (400 MHz, CDCl.sub.3: 2.27 (s, 6H), 5.21 (s, 2H), 6.94-7.02 (m, 1H), 7.08 (d, 2H), 7.41 (d, 2H), 7.82 (d, 2H), 7.87 (d, 1H), 8.30 (d, 1H), 8.60 (d, 2H)

[0311] LC/MS (method F) m/z: 553 [M+H].sup.+, R.sub.t=1.87 min.

EXAMPLE 14

Preparation of 1-(2,6-dimethylphenyl)-3-[6-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]-2-naphthyl]thiourea (compound P2.13)

[0312] ##STR00086##

[0313] This compound was prepared in a similar way as compound P2.11 (Example 10)

[0314] .sup.1H NMR (400 MHz, (CD.sub.3).sub.3SO: 2.17-2.33 (m, 6H), 6.98-7.21 (m, 3H), 7.56-7.78 (m, 3H), 7.89 -8.32 (m, 6H), 8.58-8.76 (m, 1H), 9.46 (s, 1H)

[0315] LC/MS (method E) m/z: 534 [M+H].sup.+, R.sub.t=1.62 min.

TABLE-US-00003 TABLE P1 (I-1a) [00087] wherein R.sup.a, A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5 A.sup.6, R.sup.b, R.sup.c, R.sup.d and X are as defined below: R.sup.a A.sup.1 A.sup.2 A.sup.3 A.sup.4 A.sup.5 A.sup.6 R.sup.b R.sup.c R.sup.d X LC MS/NMR Mp/ C. P1.1 OCF.sub.3 N CH CH CH CH CH CH.sub.3 H CH.sub.3 O P1.2 OCF.sub.3 N CH CH CH CH CH CH.sub.3 H CH.sub.3 S 535 [M + H].sup.+. 202-3 R.sub.t = 2.25 min Method B P1.3 OCF.sub.3 N CH CH CH CH CH iPr H H O 532.8 [M + H].sup.+. 230-5 Method D P1.4 OCF.sub.3 N CH CH CH CH CH iPr H H S 548.9 [M + H].sup.+. 215-20 Method D P1.5 OCF.sub.3 N CH CH CH CH CH CH.sub.3 H Cl S P1.6 OCF.sub.3 CH CH CH CH CH CH CH.sub.3 H CH.sub.3 S P1.7 OCF.sub.3 CH CH CH CH CH CH iPr H H S P1.8 OCF.sub.3 CH CH CH CH CH CH iPr H H O P1.9 OCF.sub.3 CH CH CH CH CH CH CH.sub.3 H Cl S P1.10 OCF.sub.3 N N CH CH CH CH CH.sub.3 H CH.sub.3 S P1.11 OCF.sub.3 N N CH CH CH CH iPr H H S P1.12 OCF.sub.3 N N CH CH CH CH iPr H H O P1.13 OCF.sub.3 N N CH CH CH CH CH.sub.3 H Cl S P1.14 OCF.sub.3 N CH N CH CH CH CH.sub.3 H CH.sub.3 S P1.15 OCF.sub.3 N CH N CH CH CH iPr H H S P1.16 OCF.sub.3 N CH N CH CH CH iPr H H O P1.17 OCF.sub.3 N CH N CH CH CH CH.sub.3 H Cl S P1.18 OCF.sub.3 N CH CH CH CH N CH.sub.3 H CH.sub.3 S P1.19 OCF.sub.3 N CH CH CH CH N iPr H H S P1.20 OCF.sub.3 N CH CH CH CH N CH.sub.3 H Cl S P1.21 OCF.sub.3 N CH CH CH CH N CH.sub.3 H Cl O P1.22 OCF.sub.3 CH CH CH CH CH N iPr H H S P1.23 OCF.sub.3 CH CH CH N CH CH iPr H H S P1.24 OCF.sub.3 CH CH N N CH CH iPr H H S

TABLE-US-00004 TABLE P2 Structure LS MS/NMR Mp/ C. P2.1 [00088] 561 (M + H).sup.+ R.sub.t = 2.47 min Method B 102-3 P2.2 [00089] 587 (M + H).sup.+ R.sub.t = 2.26 min Method B P2.3 [00090] 589 (M + H).sup.+ R.sub.t = 2.30 min Method B P2.4 [00091] 589 (M + H).sup.+ R.sub.t = 2.24 min Method B P2.5 [00092] 536 (M + H)+ Rt = 1.72 min Method F P2.6 [00093] 520 (M + H)+ Rt = 1.68 min Method F 247-9 P2.7 [00094] 592 (M + H)+ Rt = 1.12 min Method E 196-8 P2.8 [00095] 548 (M + H)+ Rt = 1.70 min Method F 227-9 P2.9 [00096] 576 (M + H)+ Rt = 1.67 min Method F P2.10 [00097] 576 (M + H)+ Rt = 1.67 min Method F P2.11 [00098] 534 (M H)+ Rt = 1.14 min Method E 217-9 P2.12 [00099] 548 (M + H)+ Rt = 1.18 min Method E 197-9 P2.13 [00100] 534 (M + H)+ Rt = 1.62 min Method F P2.14 [00101] 553 (M + H)+ Rt = 1.79 min Method F >250 P2.15 [00102] 553 (M + H)+ Rt = 1.87 min Method F >250 P2.16 [00103] 525 (M + H)+ Rt = 1.21 min Method E P2.17 [00104] 541 (M + H)+ Rt = 1.25 min Method E >250

Biological Examples (% =Percent by Weight, Unless Otherwise Specified)

Example B1: Spodoptera littoralis (Egyptian Cotton Leaf Worm)

[0316] Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying, the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feedant effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is when at least one of mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.

[0317] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1.2, P1.4, P2.1, P2.2, P2.3, P2.4, P2.9, P2.10, P2.11, P2.12, P2.14, P2.13 and P2.17.

Example B2: Plutella xylostella (Diamond Back Moth)

[0318] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions by pipetting. After drying, the plates were infested with L2 larvae (10 to 15 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.

The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1.2, P1.3, P1.4, P2.1, P2.2, P2.3. P2.4, P2.9, P2.10, P2.11, P2.13, P2.14 and P2.17.

Example B3: Diabrotica balteata (Corn Root Worm)

[0319] Maize sprouts, placed on an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.

The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P1.2, P1.3, P1.4, P2.1, P2.2, P2.3. P2.4, P2.7, P2.9, P2.10, P2.11, P2.13 and P2.17.

Example B4: Euschistus heros

[0320] Soybean leaf on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying the leaf were infested with N-2 nymphs. The samples were assessed for growth inhibition in comparison to untreated samples 5 days after infestation.

The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2.4, P2.7 and P2.17.

Example B5: Thrips Tabaci (Onion Thrips)

[0321] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10,000 ppm DMSO stock solutions. After drying the leaf discs were infested with a thrips population of mixed ages. The samples were assessed for mortality 6 days after infestation.

The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P2.4 and P2.14.

Example B6: Frankliniella occidentalis (Western Flower Thrips)

[0322] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10,000 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 7 days after infestation.

The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P2.1, P2.2, P2.3, P2.4 and P2.12.