1-phenyl-3-piperazine-pyrazoles and pesticidal compositions of matter thereof

1. 5-diazacycloalkylpyrazole derivatives of formula (I):

wherein:

R 1 is CN, CH 3 , CF 3 , C(═N-Z)—S(O) p —(C 1 -C 4 )-alkyl or CSNH 2 ; wherein Z is H, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-haloalkyl, (C 3 -C 6 )-alkenyl, (C 3 -C 6 )-alkynyl, —(CH 2 ) q R 8 , COR 9 , CO 2 —(C 1 -C 6 )-alkyl; or S(O) p R 9

R 2 is halogen, CH 3 or NR 11 R 12 ;

R 3 is (C 1 -C 3 )-haloalkyl, (C 1 -C 3 )-haloalkoxy or SF 5 ;

R 4 (C 2 -C 6 )-alkenyl, (C 2 -C 6 )-haloalkenyl, (C 2 -C 6 )-alkynyl, (C 2 -C 6 )-haloalkynyl, CO 2 —(C 1 -C 6 )-alkyl, CO 2 —(C 3 -C 6 )-alkenyl, CO 2 —(C 3 -C 6 )-alkynyl, CO 2 —(CH 2 ) q R 8 , CO 2 —(CH 2 ) q R 10 , CONR 6 R 7 or SO 2 R 9 ; formyl, COCO 2 -(C 1 -C 6 )-alkyl or CO 2 —(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 9 , CN, NO 2 , OH, R 8 , R 10 , COR 9 , NR 6 R 7 , OR 9 and CO 2 R 9 ;

or CO—(CH 2 ) m R 8 ; or CO—(CH 2 ) m R 10 ;

or (C 1 -C 6 )-alkyl 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, S(O) p R 9 , CN, NO 2 , OH, R 10 , COR 9 , NR 6 R 7 , OR 9 , COOH and CO 2 R 9 ;

or R 8 and R 10 ;

R 5 is (C 1 -C 6 )-alkyl, or(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;

A is (C 1 -C 6 )-alkylene or (C 2 -C 6 )-alkenylene which groups are unsubstituted or substituted by one or more (C 1 -C 6 )-alkyl, (C 1 -C 6 )-haloalkyl; —COCH 2 —;, (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,(CH 2 ) q R 8 or (CH 2 ) q R 10

E is (C 2 -C 6 )-alkylene or (C 2 -C 6 )-alkenylene which groups are unsubstituted or substituted by one or more (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, (C 2 -C 6 )-haloalkynyl, (C 3 -C 7 )-cycloalkyl, (C 3 -C 7 )-cycloalkyl-(C 1 C 4 )-alkyl, (CH 2 ) q R 8 or (CH 2 ) q R 10 ;

R 6 and R 7 is each independently H, (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, (C 2 -C 6 )-haloalkynyl, (C 3 -C 7 )-cycloalkyl, (C 3 -C 7 )-cycloalkyl-(C 1 -C 4 )-alkyl, (CH 2 ) q R 8 or (CH 2 ) q R 10 ; or

R 6 and R 7 may be formed together with the attached N atom a four- to seven-membered saturated ring or a five- to seven-membered unsaturated ring, which ring optionally contains one or more additional hetero atoms in the ring which are selected from 0, S and N;

R 8 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, CN, NO 2 , S(O) p R 9 and NR 6 R 7 ;

R 9 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 8 or (CH 2 ) q R 10 ;

R 10 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 9 , OH and oxo;

R 11 and R 12 are each independently H, (C 1 -C 6 )-alkyl, (C 2 -C 6 )-alkenyl or (C 2 -C 6 )-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 8 , R 10 , (C 1 -C 6 )-alkoxy, (C 1 -C 6 )-haloalkoxy;

n, p and q are each independently zero, one or two;

m is zero, one, two or three; and

each heterocyclyl in the above-mentioned radicals is independently a heterocyclic radical having 3 to 7 ring atoms and 1, 2 or 3 hetero atoms in the ring selected from the group consisting of N, O and S;

or a pesticidally acceptable salt thereof.

2. A compound or a salt thereof as claimed in claim 1 wherein

A is (C 1 -C 4 )-alkylene which groups are unsubstituted or substituted by one or more (C 1 -C 6 )-alkyl, or (C 1 -C 6 )-haloalkyl;

E is (C 2 -C 4 )-alkylene which groups are unsubstituted or substituted by one or more (C 1 -C 6 )-alkyl, or (C 1 -C 6 )-haloalkyl.

3. A compound or a salt thereof as claimed in claim 1 wherein R 4 is selected from the group consisting of CO 2 —(C 1 -C 6 )-alkyl, CO—CO 2 —(C 1 -C 6 )-alkyl or CO—(C 1 -C 6 )-alkyl unsubstituted or substituted by one or more radicals selected from the group consisting of and CO 2 R 9 ;

and where R 8 , R 9 and p are as defined in claim 1 .

4. A compound or a salt thereof as claimed in claim 1 wherein R 1 is CN or CSNH 2 , R 2 is Cl, R 3 is CF 3 , and R 5 is CF 3 .

5. A process for the preparation of compounds of formula (I) or a salt thereof as defined in claim 1 , wherein R 1 is CN, CH 3 or CF 3 which process comprises

a) the reaction of a compound of formula (III),

wherein Hal is a halogen and wherein R 1 is CN, CH 3 or CF 3 and wherein R 2 , R 3 , R 5 , n and the other residues and values are as defined in claim 1

with a compound of formula (IV) wherein R 4 , E, A and the other residues and values are as defined in claim 1 :

in the presence of a base, or

b) the reaction of a compound of formula (I) wherein R 4 is H,

and wherein R 1 is CN, CH 3 or CF 3 and wherein R 2 , R 3 , R 5 , A, E, n and the other values and residues are as defined in claim 1

with a compound of formula (V)

R 4 -L  (V)

wherein L is a leaving group and wherein R 4 is as defined as in claim 1 in the presence of a base, and

c) if desired, converting a resulting compound of formula (I) into a pesticidally acceptable salt thereof.

6. A process for the preparation of compounds of formula (I) or a salt thereof as defined in claim 1 , wherein R 1 is C(═N-Z)-S(O) p —( C 1 -C 4 )-alkyl or CSNH 2 where Z and p are as defined in claim 1 , which process comprises

a) where R 1 is CSNH 2 reacting the corresponding compound of formula (I) wherein R 1 is CN and the other residues and values are as defined in claim 1 , with an alkali or alkaline earth metal hydrosulfide or with the reagent Ph 2 PS 2 , or

b) where R 1 is CSNH 2 reacting the corresponding compound of formula (I) wherein R 1 is CN, and the other residues and values are as defined in claim 1 , with a bis(trialkylsilyl)sulfide, in the presence of a base, or

c) where R 1 is C(═NH)—S—(C 1 -C 4 )-alkyl reacting the corresponding compound of formula (I) wherein R 1 is CSNH 2 , and the other residues and values are as defined in claim 1 , with an alkylating agent of formula (VII) or (VIII);

(C 1 -C 4 )-alkyl-L 2   (VII);

((C 1 -C 4 )-alkyl) 3 O + BF 4 −   (VIII)

where L 3 is a leaving group, or

d) where R 1 is C(═NZ)-S—(C 1 -C 4 )-alkyl, wherein Z is not H, prepared by the alkylation, acylation or sulfonylation of the corresponding compound of formula (I) wherein Z is H, and the other residues and values are as defined in claim 1 , with a compound of formula (IX):

Z-L 3   (IX)

wherein Z is defined in claim 1 with the exclusion of Z=H and wherein L 3 is a leaving group, and

e) if desired, converting a resulting compound of formula (I) into a pesticidally acceptable salt thereof.

7. A pesticidal composition comprising a compound of formula (I) or a pesticidally acceptable salt thereof as defined in claim 1 , in association with a pesticidally acceptable diluent or carrier and/or surface active agent.

8. The composition according to claim 7 , further comprising another parasiticidally effective material.

9. The composition according to claim 8 , wherein the parasiticidally effective material is an endoparasiticide, an ectoparasiticide or an endectoparasitide.

10. A method for the control of arthropods, insects, arachnids, helminths and nematodes at a locus which comprises the application of an effective amount of a compound of formula (I) or a salt thereof as claimed in claim 1 or of a composition as claimed in claim 7 .